Polycarbonate resin composition and molded article composed of the same

Abstract

To provide a polycarbonate flame retardant resin composition which is low in environmental loads, and is excellent in flame retardancy, water resistant flame retardancy and moist heat resistance.SOLUTION: A polycarbonate resin composition contains, with respect to 100 pts.wt. of (A) an aromatic polycarbonate resin (component A) containing a polycarbonate block represented by the following general formula [1], 0.01 to 0.25 pts.wt. of (B) an aromatic sulfonic acid alkali (earth) metal salt (component B) which has solubility to water at 80°C of 500 g / L or less and contains no fluoroalkyl group, 0.1 to 2 pts.wt. of (C) hydrophilic fumed silica (component C) which has a specific surface area by BET adsorption of 50 to 250 m2 / g, a saturated water absorption at 23°C / 50%RH of 0.3% or more and less than 2.0%, and is not subjected to alkylsilane surface modification treatment, and 0.05 to 1.2 pts.wt. of (D) a fluorine-containing drop preventive agent (component D).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polycarbonate resin composition and a molded article made of the same. More specifically, the present invention relates to a polycarbonate resin composition which is environmentally friendly and has excellent flame retardancy, water-resistant flame retardancy, and moist heat resistance, and which is made of an aromatic polycarbonate resin, a specific aromatic sulfonic acid alkali (earth) metal salt, a specific hydrophilic fumed silica not surface-modified with an alkylsilane, and a fluorine-containing drip-preventing agent, and which has a low environmental impact, and is excellent in flame retardancy, water-resistant flame retardancy, and moist heat resistance, and a molded article made of the same. [Background technology]

[0002] Polycarbonate resins are used in many applications, such as machine parts, automobile parts, electrical and electronic parts, and office equipment parts, due to their excellent properties such as mechanical strength, dimensional stability, and flame retardancy. With its excellent flame retardancy and impact resistance as its strengths, it has been used as the housing and exterior parts of various electronic devices. In recent years, not only is high flame retardancy required to meet the needs of thinner and smaller devices, but with the expansion of applications, sufficient performance in outdoor environments, as represented by the UL746C standard, is also required. However, at present, sufficient performance has not been obtained as a material for outdoor electrical and electronic storage boxes such as information and communication boxes, which require very high impact properties, and junction boxes for solar power generation. In addition, due to environmental load, the method of making polycarbonate resin flame retardant has changed from the use of bromine-based flame retardants to the use of phosphorus-based flame retardants and organic metal salt-based flame retardants, but the widely used perfluoroalkanesulfonic acid metal salts are a concern due to their difficulty in decomposing, and their use must also be considered.

[0003] In addition, alkali (earth) metal sulfonates are known as organic metal salts that do not contain fluoroalkyl groups. However, they have the problem of insufficient flame retardancy. There are also cases where inorganic fine particles are used in combination as a flame retardant assistant (Patent Documents 1 and 2), but the flame retardancy is insufficient despite the use of perfluorobutanesulfonic acid metal salts, and 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] JP 2007-045910 A [Patent Document 2] JP 2004-156031 A 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 flame retardancy, water-resistant flame retardancy and moist heat resistance, and a molded article made from the same. [Means for solving the problem]

[0006] As a result of intensive research to solve the above problems, the present inventors discovered that the above problems can be solved by the following configuration, and 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) not containing a 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 2The polycarbonate resin composition contains 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 saturation absorption rate of 0.3% or more and less than 2.0% at 23°C / 50%RH, and 0.05 to 1.2 parts by weight of a fluorine-containing drip prevention agent (component D) (D).

[0008] [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, and when there are a plurality of each of these groups, 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]:

[0009] [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, and 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.

[0010] (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%, and is a hydrophilic fumed silica that has not been surface-modified with alkylsilane. (Configuration 3) 3. The polycarbonate resin composition according to claim 1 or 2, wherein component B is an aromatic sulfonic acid alkali (earth) metal salt not containing a fluoroalkyl group, the solubility in water at 80° C. being 100 g / L or less. (Configuration 4) The polycarbonate resin composition according to any one of configurations 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 above 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, comprising 0.01 to 1 part by weight of an ultraviolet absorber (E) (Component E) per 100 parts by weight of Component A. (Configuration 11) 11. The polycarbonate resin composition according to any one of configurations 1 to 10, comprising 0.01 to 0.5 parts by weight of a heat stabilizer (F) (Component F) per 100 parts by weight of Component A. (Configuration 12) 12. The polycarbonate resin composition according to any one of configurations 1 to 11, wherein component C is added as a master batch 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, both having a viscosity average molecular weight of 15,000 to 23,000.

[0011] (Configuration 13) (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) not containing a 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 2The present invention relates to a method for producing a 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 saturation absorption rate of 0.3% or more and less than 2.0% at 23°C / 50% RH, and 0.05 to 1.2 parts by weight of a fluorine-containing drip prevention agent (component D).

[0012] [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, and when there are a plurality of each of these groups, 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]:

[0013] [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, and 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.

[0014] (Configuration 14) 13. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 12. Effect of the Invention

[0015] The polycarbonate resin composition of the present invention has low environmental impact and excellent flame retardancy, water-resistant flame retardancy, and moist heat resistance, specifically, has good 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 applications such as various electronic and electrical device parts, camera parts, OA device parts, precision machine parts, machine parts, vehicle parts, and other agricultural materials, transport containers, play equipment, and miscellaneous goods, and the industrial effects it provides are exceptional. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] (Component A: aromatic polycarbonate resin) The aromatic polycarbonate resin in the present invention contains a polycarbonate block represented by the following general formula [1].

[0017] [ka] (In the above general formula [1], R 1 and R 2each 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, and when there are a plurality of each of these groups, 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]:

[0018] [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 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, and 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.

[0019] 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 ... 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'-dihydroxydiphenylmethane, 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, which has excellent strength and good durability, is the most suitable. These may be used alone or in combination of two or more kinds.

[0020] The viscosity average molecular weight of component A is preferably 10,000 to 30,000, more preferably 13,000 to 27,000, further preferably 15,000 to 25,000, and particularly preferably 18,000 to 23,000. If the viscosity average molecular weight of component A is less than 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 is high and generally high molding processing temperatures are required, which may lead to problems such as thermal degradation of the resin.

[0021] (Component B: Alkaline (earth) metal salt of aromatic sulfonic acid not containing a fluoroalkyl group) The polycarbonate resin composition of the present invention contains an aromatic sulfonic acid alkali (earth) metal salt not containing a fluoroalkyl group as component B. The sulfonic acid alkali (earth) metal salt is very useful in that it maintains the heat resistance of the polycarbonate resin to a large extent. The sulfonic acid alkali (earth) metal salt also includes a fluorine-substituted organic sulfonic acid alkali (earth) metal salt, but the aromatic sulfonic acid alkali (earth) metal salt not containing a fluoroalkyl group is used as component B of the present invention in view of environmental load.

[0022] 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, relative to 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, whereas if it exceeds 0.25 part by weight, flame retardancy and moist heat resistance are poor.

[0023] The solubility of component B in water at 80°C is 500g / L or less, more preferably 100g / L or less, and even more preferably 75g / L or less. If the solubility exceeds 500g / L, the component B will flow out or re-aggregate due to 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 5g / L or more. The solubility was evaluated by adding component B slowly with stirring to a glass container equipped with a stirrer, leaving the container in a hot bath at 80°C and allowing it to stand for a sufficient period of time, and then adding the component B to the container while slowly stirring the container.

[0024] Examples of the metal salt include alkali metal salts of aromatic sulfonic acid and alkaline earth metal salts of aromatic sulfonic acid (none 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 acid are preferred, and potassium salts are particularly preferred.

[0025] 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 monomeric or polymeric aromatic sulfide sulfonic acids, aromatic carboxylic acids and ester sulfonic acids, monomeric or polymeric aromatic ether sulfonic acids, aromatic sulfonate sulfonic acids, monomeric or polymeric aromatic sulfonic acids, monomeric or polymeric aromatic sulfone sulfonic acids, aromatic ketone sulfonic acids, heterocyclic sulfonic acids, aromatic sulfoxide sulfonic acids, and condensates of aromatic sulfonic acids with methylene bonds, and these may be used alone or in combination of two or more kinds.

[0026] Specific examples of the aromatic sulfonic acid alkali (earth) metal salts 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, benzenesulfonate, sodium ... Examples of the sulfonate 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.

[0027] (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 containing 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.

[0028] The fumed silica used in the present invention is amorphous silicon dioxide synthesized by dry method, and is synthesized by high-temperature hydrolysis of silicon halide in oxyhydrogen flame.Generally, fumed silica is surface-modified with hydrophobic silane such as chlorosilane, alkoxysilane, hydrosilane, silylamine, silane coupling agent, polyorganosiloxane, etc., in order to improve dispersibility and function, but in the present invention, it is necessary to use hydrophilic fumed silica without alkylsilane surface modification.Hydrophilic fumed silica without alkylsilane surface modification improves strength and exhibits flame retardancy through strong interaction with polycarbonate resin, while hydrophobic fumed silica with alkylsilane surface modification has poor dispersion in polycarbonate resin, so it has poor moist heat resistance, and also does not improve flame retardancy due to the combustibility of surface modification components.

[0029] The specific surface area of ​​component C in BET adsorption is 50 to 250 m 2 / g, preferably 100 to 230 m 2 / g, more preferably 120 to 220m 2 / g. The specific surface area of ​​component C in BET adsorption is 50 m 2 / g or less, 250m 2 When the specific surface area exceeds 1 / 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 the surface area of ​​the sample is calculated from the amount of nitrogen adsorbed and desorbed by the BET single point method, and then the specific surface area is calculated by dividing the surface area by the weight.

[0030] The saturated water absorption rate of the C component 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%. In order to make the saturated water absorption rate at 23°C / 50%RH less than 0.3%, an alkylsilane surface modification treatment is necessary, so there is no hydrophilic fumed silica that has a saturated water absorption rate at 23°C / 50%RH less than 0.3% without an alkylsilane surface modification treatment. On the other hand, if the saturated water absorption rate at 23°C / 50%RH is 2.0% or more, the flame retardancy is insufficient. The fumed silica used in the present invention exhibits an effect of suppressing combustion due to surface adsorbed water, while if the adsorbed water is excessive, hydrolysis is promoted and flammability is likely to increase, so it is considered important to set it in an appropriate range. The saturated water absorption was measured by using a TA-instruments Hi-Res TGA2950 Thermogravimetric Analyzer to measure the weight loss of a sample from room temperature to 220°C when the sample was heated from room temperature to 900°C at a rate of 10°C / min in an air atmosphere, after the sample had been sufficiently conditioned at 23°C / 50%RH for 168 hours or more.

[0031] 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, relative to 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.

[0032] 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 rate at 23°C / 50%RH is 0.3% or more and less than 2.0% and the saturation water absorption rate at 23°C / 50%RH is not alkylsilane surface modified. Specifically, a method of supplying a silane compound to a reactor and burning or hydrolyzing it in a flame can be mentioned. For example, the methods described in JP-B-47-46274, JP-B-58-54085, JP-A-59-169922, JP-A-59-184721, and JP-A-60-011218 can be referred to.

[0033] Fumed silica is produced by feeding a raw material gas containing a silane compound into a flame in a reaction process, and burning or hydrolyzing the silane compound in the flame. The fumed silica produced in the reaction process is cooled in a cooling process and then sent to a separation and recovery process. In this process, the solid content is separated from the reaction gas and recovered, and then deoxidized in a deoxidation process as necessary. The fumed silica thus obtained has a bulk density of about 0.02 g / cm. 3 Since it is a small powder, if it were to be packaged and used as is, the packaging and transportation costs of the product would be high, and the powder has a high tendency to scatter, making it difficult to handle, it is possible to adjust the bulk density significantly during the compression process.

[0034] In the present invention, the component C is preferably added as a master batch in which it is extrusion mixed in advance with the component A. By using a master batch, the powder scattering of the component C is suppressed, improving the handling properties, and the dispersibility is further improved, which may result in stable flame retardancy.

[0035] When component C is used as a master batch, 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 master batch is impaired, and if the ratio of component C exceeds the upper limit, the extrusion mixing processability of the master batch may be poor.

[0036] When component C is used as a master batch, the viscosity average molecular weight of component A is preferably 15,000 to 23,000, and more preferably 15,000 to 20,000. If the viscosity average molecular weight is below the lower limit, extrusion productivity is poor, and if it exceeds the upper limit, the extrusion processing temperature becomes very high, which may lead to deterioration of component A and cause problems in flame retardancy and color appearance.

[0037] 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."

[0038] (Component D: Fluorine-containing drip prevention agent) The polycarbonate resin composition of the present invention contains a fluorine-containing drip-preventing agent as component D. By containing this fluorine-containing drip-preventing agent, good flame retardancy can be achieved without impairing the physical properties of the molded article.

[0039] Examples of the fluorine-containing drip prevention agent include fluorine-containing polymers having fibril-forming ability, and examples of such polymers include polytetrafluoroethylene, tetrafluoroethylene copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymers, etc.), partially fluorinated polymers as shown in U.S. Patent No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, etc. Among these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0040] The molecular weight of the fibril-forming PTFE is extremely high, and it shows a tendency to bond PTFE to each other and become fibrous by external action such as shear force. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million, in terms of number average molecular weight calculated from the standard specific gravity. Such PTFE can be used in the form of a solid or an aqueous dispersion. In addition, such fibril-forming PTFE can be used in the form of a PTFE mixture mixed with other resins to improve dispersibility in resins and obtain better flame retardancy and mechanical properties.

[0041] Commercially available PTFE products having such fibril-forming ability include, for example, Teflon (registered trademark) 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 dispersions of PTFE 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 (registered trademark) 30J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.

[0042] The mixed form of PTFE can be prepared by (1) mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a co-aggregated mixture (methods described in JP-A-60-258263, JP-A-63-154744, etc.), (2) mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in JP-A-4-272957), or (3) homogeneously 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 dispersion of PTFE (method described in JP-A-06-220210, JP-A-08-188653, etc.), and (5) a method of uniformly mixing an aqueous dispersion of PTFE 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 products of these mixed forms of PTFE include "Metabrene A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

[0043] The ratio of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, in 100% by weight of the PTFE mixture. When the ratio of PTFE is within this range, good dispersibility of PTFE can be achieved. The ratio of the above E component indicates the net amount of the drip prevention agent, and in the case of the mixed form PTFE, indicates the net amount of PTFE.

[0044] The content of component D is 0.05 to 1.2 parts by weight, preferably 0.1 to 1.0 parts by weight, more preferably 0.1 to 0.8 parts by weight, and further preferably 0.15 to 0.5 parts by weight, relative to 100 parts by weight of component A. If the content of component D is less than 0.05 parts by weight, the flame retardancy becomes insufficient, and 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.

[0045] (Component E: UV absorber) The polycarbonate resin composition of the present invention can contain an ultraviolet absorbing agent as component E in order to suppress ultraviolet degradation in outdoor applications.Specific examples of the ultraviolet absorbing agent include benzophenone-based agents 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 ultraviolet absorbers 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 copolymer include 2-hydroxyphenyl-2H-benzotriazole skeleton such as 2-(2-hydroxy-5-acryloxyethylphenyl)-2H-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, and copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with the monomer.Specific examples of the ultraviolet absorber include, in the hydroxyphenyltriazine series, 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 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 the ultraviolet absorbent include cyclic iminoesters such as 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-m-phenylenebis(3,1-benzoxazine-4-one), and 2,2'-p,p'-diphenylenebis(3,1-benzoxazine-4-one). Specific examples of the ultraviolet absorbent include cyanoacrylates such as 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 polymer type ultraviolet absorber obtained by copolymerizing such an ultraviolet absorbing monomer and / or a light stable 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 the above, benzotriazole and hydroxyphenyltriazine are preferred in terms of ultraviolet absorbing ability, and cyclic iminoester and cyanoacrylate are preferred in terms of heat resistance and color. Specific examples include "Chemisorb 79" from Chemipro Chemical Co., Ltd. and "Tinuvin 234" from BASF Japan Ltd. The ultraviolet absorbing agents may be used alone or in a mixture of two or more kinds.

[0046] The content of component E is preferably 0.01 to 1 part by weight, more preferably 0.01 to 0.8 parts by weight, further preferably 0.05 to 0.6 parts by weight, and particularly preferably 0.05 to 0.5 parts by weight, relative to 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.

[0047] (Component F: Heat stabilizer) The polycarbonate resin composition of the present invention may contain a heat stabilizer to suppress thermal and oxidative degradation as Component F. The content of Component F 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, relative to 100 parts by weight of Component A.

[0048] (i) Phosphorus-based stabilizers Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and tertiary phosphines.

[0049] 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-iso-propylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, 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.

[0050] Other phosphite compounds that react with dihydric phenols to form a cyclic structure can also be used, 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.

[0051] 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, diisopropyl phosphate, and the like, and preferably triphenyl phosphate and trimethyl phosphate.

[0052] Examples of the 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-phenylphosphonite, bis Examples of the phosphonite 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, and tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such phosphonite compounds can be used in combination with the phosphite compounds having an aryl group substituted with two or more alkyl groups, and are therefore preferred.

[0053] Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0054] 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.

[0055] The phosphorus-based stabilizer may be used alone 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.

[0056] [ka] (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.)

[0057] 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.), and either of these can be used.

[0058] Among the above formula [3], more suitable phosphite compounds 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.

[0059] 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), Ultranox P626 (trademark, manufactured by Accu Standard Inc.), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgaofos 126 and 126FF (trademarks, manufactured by BASF Japan Co., 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 can be easily used. 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., Ltd.), and either can be used.

[0060] (ii) Hindered phenol antioxidants As the hindered phenol compound, various compounds that are usually blended in resins can be used. Examples of such hindered phenol compounds include α-tocopherol, butyl hydroxytoluene, 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-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 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'-hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] 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 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- (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 are examples.

[0061] 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 preferably used in the present invention. In particular, 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 preferred. The above hindered phenol-based antioxidants can be used alone or in combination of two or more.

[0062] It is preferable to use either a phosphorus-based stabilizer or a hindered phenol-based antioxidant, and more preferably to use them in combination. In the case of 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.

[0063] (iii) Other heat stabilizers The resin composition of the present invention may contain other heat stabilizers other than the phosphorus-based stabilizer and the hindered phenol-based antioxidant. Such other heat stabilizers are preferably used in combination with either one of these stabilizers and antioxidants, and particularly preferably used 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). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by BASF Japan Co., Ltd.), and this compound can be used. Furthermore, stabilizers in which this compound is mixed with various phosphite compounds and hindered phenol compounds are commercially available. Suitable examples include Irganox HP-2921 manufactured by the above company. Such premixed stabilizers can also be used in the present invention.

[0064] Other examples of the stabilizer 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 applied to rotational molding.

[0065] (Other additives) The polycarbonate resin composition of the present invention preferably contains the additives described below according to the intended use.

[0066] (i) Release agent The polycarbonate resin composition of the present invention preferably further contains a mold release agent for the purpose of improving the productivity during molding and reducing distortion of the molded product. As such a mold release agent, a known one can be used. For example, 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 modification can also be used), silicone compounds, fluorine compounds (fluorine oils represented by polyfluoroalkyl ethers, etc.), paraffin wax, beeswax, etc. can be mentioned. Among them, fatty acid esters can be mentioned as a preferred mold release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such aliphatic alcohols may be monohydric alcohols or polyhydric alcohols having dihydric or higher valences. The carbon number of the alcohol is in the range of 3 to 32, more preferably in the range of 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, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, polyhydric alcohols are more preferred.

[0067] 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, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, the aliphatic carboxylic acid is preferably one having 14 to 20 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred.

[0068] The above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural oils and fats such as animal oils and fats such as beef tallow and lard, and vegetable oils and fats such as 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 produced from such natural oils and fats and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used.

[0069] 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 and tend to 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.

[0070] 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 further preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the A component. In this range, the polycarbonate resin composition may have good mold releasability and roll releasability. In particular, such an amount of fatty acid ester provides a flame-retardant resin composition having good mold releasability and roll releasability without impairing good hue.

[0071] (ii) Dyes and pigments The polycarbonate resin composition of the present invention further contains various dyes and pigments, and can provide molded products that exhibit a variety of designs. Examples of dyes and pigments 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 a better metallic color. Aluminum powder is suitable as the metallic pigment. In addition, by blending a fluorescent brightener or other fluorescent dye that emits light, a better design effect that makes use of the luminous color can be imparted.

[0072] (iii) Fluorescent whitening agents In the resin composition of the present invention, the fluorescent brightener 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, and examples thereof 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 Company's "HAKKOL PSR." Here, the fluorescent brightener has the effect of absorbing ultraviolet energy of light and radiating this energy 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, based on 100 parts by weight of the A component. Even if the content exceeds 0.1 parts by weight, the effect of improving the color tone of the composition may be small.

[0073] (iv) Compounds capable of absorbing heat rays The polycarbonate resin composition of the present invention may contain a compound having heat absorbing ability. Suitable examples of such compounds include phthalocyanine-based near infrared absorbing agents, metal oxide-based near infrared absorbing agents such as ATO, ITO, iridium oxide, ruthenium oxide, immonium oxide, and titanium oxide, various metal compounds having excellent near infrared absorbing ability such as metal boride-based and tungsten oxide-based near infrared absorbing agents such as lanthanum boride, cerium boride, and tungsten boride, and carbon fillers. As such phthalocyanine-based near infrared absorbing agents, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of carbon fillers include carbon black, graphite (both natural and artificial), and fullerene, and preferably carbon black and graphite. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near infrared absorbing agent 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 absorbing agent, the metal boride-based near infrared absorbing agent, and the carbon filler are preferably in the range of 0.1 to 200 ppm (weight ratio), and more preferably in the range of 0.5 to 100 ppm, in the polycarbonate resin composition of the present invention.

[0074] (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 polymer fine particles, inorganic fine particles with a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles already known as light diffusing agents for polycarbonate resins. More preferred examples include acrylic crosslinked particles with a particle size of several μm and silicone crosslinked particles represented by polyorganosilsesquioxane. Examples of the shape of the light diffusing agent include spherical, discoid, columnar, and amorphous shapes. Such a sphere does not need to be a perfect sphere and includes deformed ones, and such a columnar shape includes a cube. A preferred light diffusing agent is spherical, and the more uniform the particle size, the more preferred it is. 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, relative to 100 parts by weight of component A. Two or more types of light diffusing agents can be used in combination.

[0075] (vi) Highly light-reflecting white pigments The polycarbonate resin composition of the present invention can contain a highly light-reflective white pigment to impart a light-reflecting effect. Titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferred as such a white pigment. The content of such highly light-reflective 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-reflective white pigments can be used in combination.

[0076] (vii) Antistatic agents The polycarbonate resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) organic sulfonate phosphonium salts such as arylsulfonate phosphonium salts, typified by dodecylbenzenesulfonate phosphonium salts, and alkylsulfonate phosphonium salts, as well as borate phosphonium salts such as tetrafluoroborate phosphonium salts. The content of the phosphonium salt is appropriately 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, relative to 100 parts by weight of the resin component. Examples of the antistatic agent 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, such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the alkali (earth) metal salt of organic sulfonic acid 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.

[0077] Examples of the antistatic agent include (3) organic ammonium sulfonates such as ammonium alkylsulfonates and ammonium arylsulfonates. The amount of the ammonium salt is preferably 0.05 parts by weight or less based on 100 parts by weight of the resin component. Examples of the antistatic agent include (4) polymers containing a poly(oxyalkylene) glycol component as a constituent component, such as polyether ester amide. The amount of the polymer is preferably 5 parts by weight or less based on 100 parts by weight of the resin component.

[0078] (viii) Filling material The polycarbonate resin composition of the present invention can contain various fillers known as reinforcing fillers. As such fillers, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, the fibrous filler is a filler having a fibrous shape (including rod-like, needle-like, or a shape in which the axis extends in multiple directions), and the plate-like filler is a filler having a plate-like shape (including a filler having an uneven surface or a filler having a curved plate). The granular filler is a filler having a shape other than these, including an indefinite shape. The above-mentioned fibrous or plate-like shapes are often clear from observation of the shape of the filler, but for example, as a difference from the so-called indefinite shape, a filler having an aspect ratio of 3 or more can be said to be fibrous or plate-like.

[0079] Preferred examples of the plate-like filler 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 different materials such as metals and metal oxides. The particle size is preferably in the range of 0.1 to 300 μm. The particle size refers to the value of the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase precipitation methods, in the region up to about 10 μm, the value of the median diameter (D50) of the particle size distribution measured by the laser diffraction / scattering method in the region of 10 to 50 μm, and the value of the vibration sieving method in the region of 50 to 300 μm. The particle size is the particle size in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane-, titanate-, aluminate-, and zirconate-based coupling agents, or may be in the form of granules that have been bundled or compressed with various resins such as olefin-, styrene-, acrylic-, polyester-, epoxy-, and urethane-based resins, or higher fatty acid esters.

[0080] 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. Meanwhile, 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 an image 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 fibers, flat cross-section glass fibers, milled glass fibers, carbon fibers, milled carbon fibers, metal fibers, asbestos, rock wool, ceramic fibers, slag fibers, 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, typified by heat-resistant organic fibers such as aramid fibers, polyimide fibers, and polybenzothiazole fibers, as well as fibrous fillers in which the surface of these fillers is coated with a different material such as a metal or metal oxide. Examples of fillers in which a different material is coated on the surface include metal-coated glass fibers, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fibers. The method of surface coating of different materials is not particularly limited, and examples thereof include various known plating methods (e.g., electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition, ion plating, CVD (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD, and sputtering. Here, the 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, and preferably 200. The aspect ratio of such a filler is the value in the resin composition.The flat cross-section glass fiber is a glass fiber having an average major axis of 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and an average major axis to minor axis ratio (major axis / minor axis) of 1.5 to 8, preferably 2 to 6, and even more preferably 2.5 to 5. The fibrous filler may be surface-treated with various coupling agents, bundled with various resins, and granulated by compression, in the same manner as the plate-like filler. The content of such a filler is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, even more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less, relative to 100 parts by weight of component A.

[0081] (ix) Other resins and elastomers In the polycarbonate resin composition of the present invention, other resins or elastomers may be used in small proportions in place of a part of the resin component of component A, as long as the effects of the present invention are exhibited. The amount of the other resins or elastomers 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 with 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.

[0082] (x) Other additives The polycarbonate resin composition of the present invention may contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents, and the like.

[0083] <Production of Resin Composition> Any method may be adopted for producing the polycarbonate resin composition of the present invention. For example, the A component, B component, C component, D component, and optionally other components are thoroughly mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, or an extrusion mixer, and then granulated as necessary using an extrusion granulator or a briquetting machine, followed by melt kneading using a melt kneader such as a vented twin-screw extruder, and pelletizing using equipment such as a pelletizer.

[0084] <Production of molded products> The polycarbonate resin composition of the present invention can be obtained by injection molding such pellets. In such injection molding, not only the usual cold runner type molding method but also hot runners that enable runnerless production can be used. In addition, in the injection molding, not only usual molding methods but also 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, heat insulating mold molding, in-mold remelting molding, and molding methods consisting of combinations of these can be used.

[0085] In addition, the polycarbonate resin composition of the present invention can be directly made into a sheet, film, irregular extrusion molded product, direct blow molded product, and injection molded product by melt-kneading the resin in an extruder without going through pellets. The polycarbonate resin composition of the present invention can also be used in the form of various irregular extrusion molded products, sheets, films, etc. by extrusion molding. Inflation method, calendar method, casting method, etc. can also be used for molding sheets and films. Furthermore, it is possible to mold it into a heat-shrinkable tube by subjecting it to a specific stretching operation, or to make a molded product by rotational molding, blow molding, etc.

[0086] 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.).

[0087] (Flame retardant) The flame retardancy of the polycarbonate resin composition of the present invention was evaluated by carrying out a vertical flame test on UL test pieces (width 13 mm × length 125 mm × thickness 1.0 mm and 0.8 mm) prepared in accordance with the UL94 flame test, and classifying the maximum burning time, total burning time, number of drips accompanied by cotton ignition (number of drips), and the other grades into V-0, V-1, V-2, and Not-V according to the standard. V-0 at 1.0 mm is preferable as excellent flame retardancy, and V-0 at 0.8 mm is more preferable.

[0088] (Water and flame resistant) The weather resistance and flame retardancy of the polycarbonate resin composition of the present invention was evaluated in accordance with the UL746C weather resistance test, by subjecting the above-mentioned UL test piece to a hot water exposure test and then a vertical combustion test, and by classifying the maximum burning time, total burning time, number of drips accompanied by cotton ignition (number of drips) and the other into V-0, V-1, V-2 and Not-V according to the standard. The hot water exposure test here refers to a treatment in which a molded product is immersed in ion-exchanged water heated to 82°C for 168 hours. Note that the condition was adjusted from the hot water exposure test to the vertical combustion test by keeping the product in an environment of 23°C / 50%RH for 48 hours or more. It is preferable that the product is V-0 even after the hot water exposure test, since it has excellent water resistance and flame retardancy.

[0089] (Moisture and heat resistance) The wet 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 thermo-hygrostat maintained at 90°C / 95%RH, and then measuring the light transmittance in accordance with JIS K 7361 using HM-150N manufactured by Murakami Color Research Laboratory Co., Ltd. The light transmittance value is preferably 40% or more in view of excellent appearance stability over long-term use, and more preferably 60% or more. EXAMPLES

[0090] The present invention will be described in more detail below with reference to examples, but these are not intended to limit the present invention. Unless otherwise specified, parts in the examples are parts by weight and % is % by weight. Evaluations were performed according to the following methods.

[0091] (1) Viscosity average molecular weight (Mv) The viscosity average molecular weight of the A component of the present invention was calculated as follows. The resin composition pellets were mixed with 20 to 30 parts by weight of methylene chloride to dissolve the soluble content in the A component. The soluble content was collected by removing the insoluble content by celite filtration. Thereafter, the solvent in the obtained solution was removed by heating and thoroughly dried to obtain the solid content of the component in the A component that was soluble in methylene chloride. 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 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

[0092] (2) Flame retardancy (UL94 vertical flame test) The pellets of the resin composition were dried with hot air at 120°C for 5 hours, and then UL test pieces (width 13 mm x length 125 mm x thickness 1.0 mm and 0.8 mm) were produced using an injection molding machine at a molding temperature of 300 to 320°C, a mold temperature of 70°C, and a molding cycle of 30 seconds. Using the obtained UL test pieces, a vertical combustion test was carried out in accordance with UL94.

[0093] (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 in until the UL test specimen was fully immersed. It was then transferred to a thermostatic chamber maintained at 80°C, and subjected to hot water exposure treatment for 168 hours. After the test period was over, the test specimen was taken out and kept in an environment of 23°C / 50% RH for 48 hours or more to condition it, and then a vertical flame test was performed in accordance with UL94.

[0094] (4) Moisture and heat resistance The pellets of the resin composition were dried with hot air at 120°C for 5 hours, and then molded plates (width 50mm x length 100mm x thickness 2.0mm) were produced 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. The obtained plate was then treated for 500 hours in a constant temperature and humidity layer maintained at 90°C / 95%RH. The light transmittance of the molded plate before and after the treatment was measured using HM-150N manufactured by Murakami Color Research Laboratory Co., Ltd. in accordance with JIS K 7361.

[0095] [Raw materials 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 skeleton of 2,2-bis(4-hydroxyphenyl)propane (Teijin Ltd. Panlite L-1225WX) 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)

[0096] (Component B: Alkaline (earth) metal salt of aromatic sulfonic acid not containing a fluoroalkyl group) B-1: Potassium diphenylsulfone-3-sulfonate (solubility in water at 80°C: 50g / L) B-2: Polystyrene-Polystyrene Sulfonic Acid Potassium Salt Copolymer (PSS-K, manufactured by Sony Chemical & Information Devices Corporation, insoluble in water at 80°C) B-3 (Comparative Example): Sodium p-toluenesulfonate (ARiCHEM, NATS-FR manufactured by LCC, solubility in water at 80°C > 500g / L)

[0097] (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 (manufactured by 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 (Comparative Example): 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 4.0%) C-6 (Comparative Example): QS-30 (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 (Comparative Example): 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%)

[0098] (Component D: Fluorine-containing drip prevention agent) D-1: SN3307PF (polytetrafluoroethylene coated with styrene-acrylonitrile copolymer, polytetrafluoroethylene content 50% by weight, manufactured by Shine Polymers)

[0099] (Component E: UV absorber) E-1: UV absorber (ADEKA STAB LA-31 (product name) manufactured by ADEKA Corporation)

[0100] (Component F: Heat stabilizer) F-1: 3-(3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate (manufactured by BASF Japan Ltd.: Irganox 1076 (trade name)) F-2: Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos168 (trade name) manufactured by BASF Japan Ltd.)

[0101] [Examples 1 to 13, Comparative Examples 1 to 10] [Production of polycarbonate resin composition] The components A to D and various additives were weighed according to the compositions shown in Tables 1 and 2, mixed uniformly using a blender, and melt-kneaded using 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 in advance at a concentration of 10 to 100 times the blending amount, and then the entire mixture was mixed using a blender. The vented twin-screw extruder used was a KTX-30 (diameter 30 mmφ) made by Kobe Steel, Ltd. The strands were extruded under the conditions of cylinder temperature and die temperature of 280°C, screw rotation speed of 150 rpm, discharge rate of 20 kg / h, and vent suction degree of 3 kPa, and after cooling in a water bath, the strands were cut using a pelletizer and pelletized. The results of various evaluations are shown in Tables 1 and 2. In Example 12, the C-3 component was added as a master batch pellet obtained by extrusion mastering a linear aromatic polycarbonate resin powder (Panlite CM-1000 manufactured by Teijin Limited) having a viscosity average molecular weight of 16,000 and a repeating skeleton of 2,2-bis(4-hydroxyphenyl)propane and the C-3 component in a ratio of 80:20 parts by weight using a vented twin-screw extruder (TEX30α manufactured by Japan Steel Works, Ltd.) at a cylinder temperature of 270° C. The A component in Example 12 contains the polycarbonate resin contained in the master batch.

[0102] [Table 1]

[0103] [Table 2]

[0104] As is clear from the above table, the compositions of Examples 1 to 13 achieved V-0 in the UL94 vertical flame test at thicknesses of 0.8 mm and 1.0 mm, and further maintained 1.0 mm V-0 in water resistance and flame retardancy after exposure to hot water, and also showed excellent moist heat resistance at 90°C / 95% RH / 500 h.

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) not containing a 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 of 0.3% or more and less than 2.0% at 23°C / 50% RH, the 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 0.05 to 1.2 parts by weight of a fluorine-containing drip-preventing agent (component D) (D). 【Chemistry 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, and when there are a plurality of each of these groups, 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]: 【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, and 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, and has a water saturation absorption rate of 0.5% or more and less than 1.5% at 23° C. / 50% RH.

3. 3. 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 salt having a solubility in water at 80° C. of 100 g / L or less.

4. 3. 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. 3. The polycarbonate resin composition according to claim 1, wherein the content of the component B is 0.03 to 0.15 parts by weight per 100 parts by weight of the component A.

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

7. 3. 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. 3. The polycarbonate resin composition according to claim 1, wherein the content of the component C is 0.3 to 1.0 part by weight per 100 parts by weight of the component A.

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

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

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

12. 3. The polycarbonate resin composition according to claim 1, wherein the component C is added as a master batch obtained by extrusion mixing in advance in a ratio of 95 to 20 parts by weight of the component A and 5 to 80 parts by weight of the component C, both having a viscosity average molecular weight of 15,000 to 23,000.

13. (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) not containing a 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 of 0.3% or more and less than 2.0% at 23°C / 50% RH, the method comprising the steps of: (A) hydrophilic fumed silica (component C) not surface-modified with alkylsilane; and (B) 0.05 to 1.2 parts by weight of a fluorine-containing drip-preventing agent (component D). 【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, and when there are a plurality of each of these groups, 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]: 【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, and 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.

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

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