Polycarbonate resin composition

Abstract

To provide a polycarbonate resin composition that exhibits high flame retardancy and also provides superior thermal stability, resistance to humid heat, and flowability.SOLUTION: A polycarbonate resin composition comprises, relative to 100 pts.mass of a polycarbonate resin (A), 0.01-0.5 pts.mass of a metal salt of an organic sulfonic acid (B), 0.001-0.08 pts.mass of an alicyclic epoxy compound (C), and 0-0.10 pts.mass of a phosphorus-based thermal stabilizer, wherein a ratio (C) / (B) of the contents of the metal salt of the organic sulfonic acid (B) and the alicyclic epoxy compound (C) is 0 or more and less than 1.0, and silicone compounds are absent or, if present, are less than 0.01 pts.mass relative to 100 pts.mass of the polycarbonate resin (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition having high flame retardancy, excellent thermal stability and moist heat resistance, and also excellent flowability. [Background technology]

[0002] Polycarbonate resins are resins with excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, as materials for manufacturing vehicle parts, electrical and electronic equipment parts, housing materials, and other industrial parts. In particular, flame-retardant polycarbonate resin compositions are suitably used as vehicle parts, electrical and electronic equipment parts such as personal computers, mobile phones, and battery cases, and parts for office automation and information equipment such as printers and copiers.

[0003] In recent years, there has been an increasing trend towards flame retardancy, and polycarbonate resins are now required to have a high level of flame retardancy, with many cases requiring V-0 products under the UL-94 test method. Halogen-based flame retardants and phosphorus-based flame retardants have been used to impart flame retardancy to polycarbonate resins. However, in order to achieve V-0 flame retardancy using phosphorus-based flame retardants, a relatively high addition rate is required, which tends to reduce the mechanical properties of polycarbonate resin materials. Flame retardancy using halogen-based bromine-based or chlorine-based flame retardants is being banned under stricter regulations due to the toxicity and environmental issues caused by the emission of harmful gases.

[0004] Fluorine-based flame retardants, such as the perfluoroalkane metal salts proposed in Patent Documents 1 and 2, are effective flame retardants because they provide high levels of flame retardancy with a relatively small amount. However, in recent years, fluorine compounds have become subject to international restrictions, particularly in Europe and the United States, and PFAS restrictions on perfluoroalkyl and polyfluoroalkyl compounds are being implemented primarily in the EU and the United States, and are becoming even stricter internationally, including in Japan. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 47-40445 [Patent Document 2] Japanese Patent Application Publication No. 49-88943 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, there is a strong demand for an environmentally friendly flame-retardant polycarbonate resin composition that does not generate toxic gases during combustion, meets various regulations such as PFAS regulations, etc. Organic sulfonate metal salts, typified by potassium diphenylsulfone sulfonate, are effective flame retardants in this regard, but have been found to have poor thermal stability. [Means for solving the problem]

[0007] Means for Solving the Problems The present inventors have conducted extensive research to achieve the above object and have found that the use of an alicyclic epoxy compound in combination with an organic sulfonic acid metal salt improves thermal stability and also improves moist heat resistance, thereby completing the present invention. The present invention relates to the following polycarbonate resin composition and molded article.

[0008] 1. A polycarbonate resin composition comprising, per 100 parts by mass of polycarbonate resin (A), 0.01 to 0.5 parts by mass of an organic sulfonate metal salt (B), 0.001 to 0.08 parts by mass of an alicyclic epoxy compound (C), and 0 to 0.10 parts by mass of a phosphorus-based heat stabilizer, wherein the content ratio (C) / (B) of the organic sulfonate metal salt (B) to the alicyclic epoxy compound (C) is 0 to less than 1.0, and the composition does not contain a silicone compound, or if it contains a silicone compound, the amount of the silicone compound is less than 0.01 part by mass per 100 parts by mass of polycarbonate resin (A). 2. The polycarbonate resin composition according to the above item 1, further comprising a phosphorus-based heat stabilizer (D) in an amount of more than 0 part by mass and not more than 0.10 parts by mass per 100 parts by mass of the polycarbonate resin (A). 3. Pellets of the polycarbonate resin composition according to the above item 1 or 2. 4. A molded article obtained by molding the polycarbonate resin composition according to 1 or 2 above. 5. A molded article obtained by molding the polycarbonate resin pellets described in 3 above. [Effects of the Invention]

[0009] The polycarbonate resin composition of the present invention contains an organic sulfonic acid metal salt and an alicyclic epoxy compound in specific amounts and ratios, and therefore has high flame retardancy, excellent thermal stability, moist heat resistance, and excellent fluidity (moldability). The mechanism behind this effect is presumed to be as follows. While organic metal sulfonates tend to accelerate the hydrolysis of polycarbonate resins, resulting in poor thermal stability, the alicyclic epoxy compound traps the cations of the organic metal sulfonates, thereby inhibiting the thermal decomposition of the polycarbonate resin and improving its thermal stability. Furthermore, the alicyclic epoxy compound hydrolyzes before the polycarbonate resin, further improving its moist heat resistance. Furthermore, by setting the content ratio (C) / (B) of the organic metal sulfonate (B) to the alicyclic epoxy compound (C) within the above range, the adverse effects of the diol compound generated by hydrolysis when the alicyclic epoxy compound is in excess of the organic metal sulfonate can be prevented, resulting in excellent flame retardancy, thermal stability, and moist heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below with reference to embodiments and examples. In this specification, unless otherwise specified, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0011] The polycarbonate resin composition of the present invention is characterized in that it contains 0.01 to 0.5 parts by mass of an organic sulfonate metal salt (B), 0.001 to 0.08 parts by mass of an alicyclic epoxy compound (C), and 0 to 0.10 parts by mass of a phosphorus-based heat stabilizer relative to 100 parts by mass of a polycarbonate resin (A), the ratio (C) / (B) of the contents of the organic sulfonate metal salt (B) to the alicyclic epoxy compound (C) being 0 to less than 1.0, and the composition does not contain a silicone compound, or if it contains a silicone compound, its amount is less than 0.01 part by mass relative to 100 parts by mass of the polycarbonate resin (A).

[0012] [Polycarbonate resin (A)] The polycarbonate resin (A) used in the present invention is not particularly limited, and various types can be used. Polycarbonate resins can be classified into aromatic polycarbonate resins in which the carbons directly bonded to the carbonate bonds are aromatic carbons, and aliphatic polycarbonate resins in which the carbons directly bonded to the carbonate bonds are aliphatic carbons, and either type can be used. Among these, aromatic polycarbonate resins are preferred as the polycarbonate resin (A) from the viewpoints of heat resistance, mechanical properties, electrical properties, etc.

[0013] Among the monomers that are raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include: dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (i.e., resorcinol), and 1,4-dihydroxybenzene; dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, and 4,4'-dihydroxybiphenyl;

[0014] dihydroxynaphthalenes such as 2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene;

[0015] dihydroxydiaryl ethers such as 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy)benzene, and 1,3-bis(4-hydroxyphenoxy)benzene;

[0016] 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C), 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)(4-propenylphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethane, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1,1-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)octane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane, 1,1-bis(4-hydroxyphenyl)dodecane, Bis(hydroxyaryl)alkanes such as;

[0017] 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane, Bis(hydroxyaryl)cycloalkanes such as;

[0018] 9,9-bis(4-hydroxyphenyl)fluorene, Cardo structure-containing bisphenols such as 9,9-bis(4-hydroxy-3-methylphenyl)fluorene;

[0019] 4,4'-dihydroxydiphenyl sulfide, Dihydroxydiaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfone, dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone; etc.

[0020] Of these, bis(hydroxyaryl)alkanes are preferred, and bis(4-hydroxyphenyl)alkanes are particularly preferred. In particular, from the standpoints of impact resistance and heat resistance, 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) and 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C) are preferred. The aromatic dihydroxy compounds may be used alone or in any combination of two or more in any ratio.

[0021] Among the monomers that serve as raw materials for polycarbonate resins, examples of carbonate precursors include carbonyl halides, carbonate esters, etc. The carbonate precursors may be used alone or in any combination and ratio of two or more.

[0022] Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds; and the like.

[0023] Specific examples of carbonate esters include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.

[0024] The method for producing the polycarbonate resin (A) is not particularly limited, and any method can be used. Examples include interfacial polymerization, melt transesterification, ring-opening polymerization of a cyclic carbonate compound, and solid-phase transesterification of a prepolymer. Among these, the interfacial polymerization and melt transesterification methods are preferred because they have a greater effect of improving moist heat resistance, and the interfacial polymerization method is particularly preferred.

[0025] The molecular weight of the polycarbonate resin (A), expressed as a viscosity average molecular weight (Mv) calculated from the solution viscosity measured at 25°C using methylene chloride as a solvent, is preferably 10,000 to 50,000, more preferably 11,000 to 40,000, even more preferably 12,000 to 35,000, and particularly preferably 13,000 to 30,000. By setting the viscosity average molecular weight to at least the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, and by setting the viscosity average molecular weight to at most the upper limit of the above range, the decrease in flowability of the polycarbonate resin composition of the present invention can be suppressed and improved, and molding processability can be improved, making molding process easier. Two or more polycarbonate resins having different viscosity average molecular weights may be mixed together, and in this case, polycarbonate resins having viscosity average molecular weights outside the above-mentioned preferred range may be mixed.

[0026] The viscosity average molecular weight [Mv] is calculated by using methylene chloride as a solvent and an Ubbelohde viscometer to determine the intrinsic viscosity [η] (unit: dl / g) at a temperature of 25°C, and then calculating it using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 Mv 0.83 The intrinsic viscosity [η] is the specific viscosity [η] at each solution concentration [C] (g / dl). sp ] was measured and the value was calculated according to the following formula.

number

[0027] Furthermore, in order to improve the appearance and fluidity of molded articles, the polycarbonate resin (A) may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. Furthermore, the amount of the polycarbonate oligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

[0028] Furthermore, the polycarbonate resin (A) may be not only virgin raw materials but also polycarbonate resin recycled from used products (so-called material-recycled polycarbonate resin), and it is also preferable to contain both virgin polycarbonate resin and recycled polycarbonate resin, or it may consist of recycled polycarbonate resin. When recycled polycarbonate resin is contained, the proportion of recycled polycarbonate resin in polycarbonate resin (A) is preferably 30% or more, 40% or more, 50% or more, 60% or more, or 80% or more, and it is also preferable that the recycled polycarbonate resin is 100%.

[0029] [Organosulfonic acid metal salt (B)] The polycarbonate resin composition of the present invention contains an organic sulfonic acid metal salt (B).

[0030] Examples of the metal of the organic sulfonic acid metal salt (B) include alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); alkaline earth metals such as magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba); and aluminum (Al), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), and molybdenum (Mo). In particular, alkali metals and alkaline earth metals are preferred, alkali metals are more preferred, sodium, potassium and cesium are preferred, sodium and potassium are particularly preferred, and potassium is most preferred, because they can promote the formation of a charred layer when the polycarbonate resin composition of the present invention is burned, further enhance the flame retardancy, and favorably maintain the properties of the polycarbonate resin, such as mechanical properties such as impact resistance, heat resistance and electrical properties.

[0031] Preferred examples of the organic sulfonic acid metal salt (B) include metal salts of aromatic sulfonic acids, metal salts of aromatic sulfonamides (or sulfonimides), and metal salts of polystyrene sulfonic acids.

[0032] Specific examples thereof include alkali metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule, such as potassium 3-(phenylsulfonyl)benzenesulfonate (i.e., potassium diphenylsulfone-3-sulfonate), dipotassium diphenylsulfone-3,3'-disulfonate, sodium benzenesulfonate, potassium benzenesulfonate, cesium benzenesulfonate, sodium paratoluenesulfonate, potassium paratoluenesulfonate, cesium paratoluenesulfonate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, cesium dodecylbenzenesulfonate, potassium styrenesulfonate, sodium polystyrenesulfonate, potassium polystyrenesulfonate, and cesium polystyrenesulfonate; Examples include alkaline earth metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule, such as magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, magnesium dodecylbenzenesulfonate, and calcium dodecylbenzenesulfonate.

[0033] Examples of metal salts of aromatic sulfonamides (or sulfonimides) include potassium salts of N-(p-tolylsulfonyl)-p-toluenesulfonimide, potassium salts of N-(N'-benzylaminocarbonyl)sulfanilimide, and potassium salts of N-(phenylcarboxyl)-sulfanilimide.

[0034] The organic sulfonic acid metal salt (B) also includes perfluoroalkanesulfonic acid. By combining perfluoroalkanesulfonic acid with an alicyclic epoxy compound, the thermal stability and moist heat resistance can be improved.

[0035] Examples of metal salts of perfluoroalkanesulfonic acids include alkali metal salts of perfluoroalkanesulfonic acids such as potassium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, and lithium perfluorobutanesulfonate; and alkaline earth metal salts of perfluoroalkanesulfonic acids such as magnesium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, barium perfluorobutanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, and barium trifluoromethanesulfonate. Among the perfluoroalkanesulfonic acids exemplified above, alkali metal salts of perfluoroalkanesulfonic acids are particularly preferred, and specifically, potassium perfluorobutanesulfonate, sodium perfluoroethanesulfonate, potassium trifluoromethanesulfonate, etc. are preferred.

[0036] As the organic sulfonate metal salt (B), a non-fluorine-based organic sulfonate metal salt that does not have a C—F bond in the molecule is preferred, and metal salts of paratoluenesulfonic acid, metal salts of phenylsulfonylbenzenesulfonic acid, and metal salts of polystyrenesulfonic acid are preferred, and among these, metal salts, particularly alkali metal salts, especially sodium salts or potassium salts are preferred.

[0037] The organic sulfonic acid metal salt (B) may be used alone or as a mixture of two or more kinds in any combination and ratio.

[0038] The content of the organic sulfonic acid metal salt (B) is 0.01 to 0.5 parts by mass, preferably 0.02 parts by mass or more, more preferably 0.03 parts by mass or more, 0.05 parts by mass or more, 0.08 parts by mass or more, 0.09 parts by mass or more, and particularly preferably 0.10 parts by mass or more, per 100 parts by mass of the polycarbonate resin (A), and is preferably 0.40 parts by mass or less, more preferably 0.30 parts by mass or less, more preferably 0.25 parts by mass or less, 0.20 parts by mass or less, and particularly preferably 0.18 parts by mass or less. By incorporating such an amount of the alicyclic epoxy compound (C) in combination with a predetermined amount of the alicyclic epoxy compound (C) in such a manner that the content ratio (C) / (B) of the two is from 0 to less than 1.0, a polycarbonate resin composition having high flame retardancy, thermal stability, and moist heat resistance can be obtained.

[0039] [Alicyclic epoxy compounds (C)] The aromatic polycarbonate resin composition of the present invention contains an alicyclic epoxy compound (C).

[0040] As the alicyclic epoxy compound (C), an alicyclic compound having one or more epoxy groups in one molecule is used. Specifically, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 4-(3,4-epoxy-5-methylcyclohexyl)butyl-3',4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylcyclohexylcarboxylate, bis-epoxydicyclopentadienyl ether, bis-epoxycyclohexyl adipate, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methylcyclohexylmethyl-3',4'-epoxycyclohexyl Preferred examples of the epoxy cyclohexyl include ethyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexyl carboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexyl carboxylate, octadecyl-3,4-epoxycyclohexyl carboxylate, 2-ethylhexyl-3',4'-epoxycyclohexyl carboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3',4'-epoxycyclohexyl carboxylate, diethyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, and di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate. Among these, alicyclic epoxy compounds having two or more epoxy groups in one molecule are particularly preferred, and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate is particularly preferred.

[0041] The alicyclic epoxy compound (C) may be used alone or in combination of two or more.

[0042] The content of the alicyclic epoxy compound (C) is 0.001 to 0.08 parts by mass, preferably 0.005 parts by mass or more, particularly 0.008 parts by mass or more, 0.010 parts by mass or more, 0.013 parts by mass or more, most preferably 0.015 parts by mass or more, and preferably 0.075 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). If the content of the alicyclic epoxy compound (C) is less than 0.001 parts by mass, the thermal stability and moist heat resistance effects will be insufficient, while if it exceeds 0.08 parts by mass, not only will the thermal stability and moist heat resistance effects deteriorate, but the hue may also decrease.

[0043] The ratio (C) / (B) of the content of the organic sulfonic acid metal salt (B) to the alicyclic epoxy compound (C) is 0 or more and less than 1.0. By combining the two in such a ratio, excellent thermal stability and moist heat resistance can be achieved. The ratio (C) / (B) of the content is preferably more than 0 and less than 1.0, more preferably 0.05 or more, even more preferably 0.10 or more, and particularly preferably 0.15 or more, and more preferably 0.95 or less, even more preferably 0.90 or less, 0.85 or less, and particularly preferably 0.80 or less.

[0044] The polycarbonate resin composition of the present invention does not contain a silicone compound, or if it does contain one, the amount is less than 0.01 part by mass per 100 parts by mass of the polycarbonate resin (A). By containing or not containing a silicone compound within the above range, a resin composition can be obtained that does not generate gas or mold deposits during molding. Silicone compounds are organosilicon compounds that have a siloxane bond as a backbone and have organic groups directly bonded to the silicon. Examples of the organic groups directly bonded to the silicon include methyl, ethyl, phenyl, vinyl, trifluoropropyl, and combinations thereof.

[0045] The polycarbonate resin composition of the present invention preferably contains substantially no phosphorus-based flame retardant or halogen-based flame retardant. Here, "substantially no" means that the amount of the phosphorus-based flame retardant and / or halogen-based flame retardant, individually or in total, per 100 parts by mass of the polycarbonate resin (A), is preferably less than 0.05 parts by mass, more preferably less than 0.03 parts by mass, even more preferably less than 0.01 parts by mass, less than 0.005 parts by mass, less than 0.001 parts by mass, particularly preferably less than 0.0005 parts by mass.

[0046] [Stabilizer (D)] The polycarbonate resin composition of the present invention preferably contains a stabilizer, and the stabilizer is preferably a phosphorus-based stabilizer or a phenol-based stabilizer.

[0047] Any known phosphorus stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of Group 1 or Group 2 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds, with organic phosphite compounds being particularly preferred.

[0048] Examples of organic phosphite compounds include triphenyl phosphite, tris(mononylphenyl)phosphite, tris(mononyl / dinonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, monooctyldiphenyl phosphite, dioctylmonophenyl phosphite, monodecyldiphenyl phosphite, didecylmonophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite. Examples of such organic phosphite compounds include "ADK STAB 1178," "ADK STAB 2112," and "ADK STAB HP-10" manufactured by ADEKA CORPORATION, "JP-351," "JP-360," and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd., and "IRGAFOS 168" manufactured by BASF. The phosphorus-based stabilizer may be contained either as one type or as two or more types in any combination and ratio.

[0049] The content of the phosphorus-based stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, and usually 1 part by mass or less, preferably 0.7 part by mass or less, more preferably 0.5 part by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). If the content of the phosphorus-based stabilizer is below the lower limit of the above range, the thermal stabilization effect may be insufficient, whereas if the content of the phosphorus-based stabilizer exceeds the upper limit of the above range, the effect may plateau and become uneconomical.

[0050] Examples of the phenolic stabilizer include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6- triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like.

[0051] Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Specific examples of such hindered phenol antioxidants include "Irganox 1010" and "Irganox 1076" manufactured by BASF, and "Adekastab AO-50" and "Adekastab AO-60" manufactured by ADEKA. The phenolic stabilizer may be contained in one kind or in any combination and ratio of two or more kinds.

[0052] The content of the phenolic stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). By setting the content of the phenolic stabilizer to be equal to or more than the lower limit of the above range, the effect as a phenolic stabilizer can be sufficiently obtained, and by setting the content to be equal to or less than the upper limit of the above range, the effect does not plateau and is economical.

[0053] [Filling material] The polycarbonate resin composition of the present invention preferably further contains a filler. The content of the filler is preferably 3 parts by mass or more, particularly 5 parts by mass or more, 7 parts by mass or more, or 10 parts by mass or more, per 100 parts by mass of the polycarbonate resin (A), and is preferably 80 parts by mass or less, particularly 75 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, and particularly preferably 50 parts by mass or less. The filler may be contained in one kind or in two or more kinds.

[0054] The filler is preferably an inorganic filler, and the inorganic filler may be any of an acicular inorganic filler, a fibrous inorganic filler, and a plate-like inorganic filler. An acicular inorganic filler is an inorganic filler having a whisker-like, columnar, or other shape, and examples thereof include wollastonite. A fibrous inorganic filler refers to a thin, long fibrous inorganic filler, and examples thereof include glass fiber, ceramic fiber, and carbon fiber. Examples of the shape of the fibrous inorganic filler include chopped strands and milled fibers. A plate-like inorganic filler is an inorganic filler having a flake-like, scale-like, or other shape, and examples thereof include talc, mica, and glass flakes.

[0055] The filler is preferably a glass-based filler, and preferred examples thereof include glass fiber, glass flake, glass beads, and glass balloons, with glass fiber and glass flake being more preferred, and glass fiber being particularly preferred. The raw glass composition is preferably alkali-free, and examples thereof include E glass, C glass, S glass, and R glass, with E glass being preferred.

[0056] The cross-sectional shape of the glass fiber may be a typical perfect circle or various irregular cross-sectional shapes. The number average fiber length (cut length) of the glass fiber is preferably 0.5 to 10 mm, more preferably 1.0 to 5.0 mm. The number average fiber diameter of the glass fiber is preferably 4.0 μm or more, more preferably 4.5 μm or more, and even more preferably 5.0 μm or more, with the upper limit being preferably 25 μm or less, more preferably 20 μm or less. Glass fibers having a flat cross section are also preferred, with an aspect ratio of 1.5 to 8 being more preferred, and an aspect ratio of 2 to 6 being even more preferred. The glass flakes are, for example, scale-like flakes having a thickness of 1 to 20 μm and a side length of 0.05 to 1.0 mm.

[0057] The glass-based filler is also preferably surface-treated with a surface treatment agent such as a silane coupling agent, for example, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-aminopropyltriethoxysilane. The amount of the surface treatment agent attached is preferably 0.01 to 1% by mass of the glass-based filler. Furthermore, if necessary, the glass-based filler may be surface-treated with a lubricant such as a fatty acid amide compound or silicone oil, an antistatic agent such as a quaternary ammonium salt, a film-forming resin such as an epoxy resin or urethane resin, or a mixture of a film-forming resin with a heat stabilizer, a flame retardant, or the like.

[0058] [Release agent] The resin composition of the present invention preferably contains a mold release agent. Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils.

[0059] Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids. Aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids having 6 to 36 carbon atoms, with saturated aliphatic mono-carboxylic acids having 6 to 36 carbon atoms being more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetralinic acid, montanic acid, adipic acid, and azelaic acid.

[0060] The aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol can be, for example, the same as the aliphatic carboxylic acid described above. On the other hand, the alcohol can be, for example, a saturated or unsaturated monohydric or polyhydric alcohol. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monohydric or polyhydric saturated alcohol having 30 or less carbon atoms is preferred, and an aliphatic saturated monohydric alcohol or an aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferred. Here, the term "aliphatic" is used to include alicyclic compounds.

[0061] Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol.

[0062] The ester may contain an aliphatic carboxylic acid and / or an alcohol as an impurity. The ester may be a pure substance or a mixture of multiple compounds. The aliphatic carboxylic acid and the alcohol that combine to form an ester may each be used alone or in any combination and ratio of two or more.

[0063] Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

[0064] Examples of aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Aliphatic hydrocarbons also include alicyclic hydrocarbons. These hydrocarbons may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferred, and paraffin wax and polyethylene wax are more preferred. The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less. The aliphatic hydrocarbon may be a single substance, but a mixture of substances with various constituent components and molecular weights can also be used as long as the main component is within the above range.

[0065] Examples of polysiloxane-based silicone oils include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

[0066] The above-mentioned release agents may be contained either alone or in any combination and ratio of two or more.

[0067] The content of the release agent is preferably 0.1 to 2 parts by mass, more preferably 1 part by mass or less, even more preferably 0.8 parts by mass or less, and particularly preferably 0.5 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). If the content of the release agent is less than the lower limit of the above range, the release effect tends to be insufficient, whereas if it exceeds the upper limit of the above range, there is a possibility that the hydrolysis resistance will decrease and mold contamination during injection molding will occur.

[0068] [Additives, etc.] The polycarbonate resin composition of the present invention may contain additives other than those described above, such as ultraviolet absorbers, fluorescent brighteners, pigments, dyes, plasticizers, compatibilizers, etc. These additives may be contained alone or in combination of two or more.

[0069] It is also possible to contain a resin other than the polycarbonate resin (A) in an amount less than that of the polycarbonate resin (A). Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate; styrene-based resins such as polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin); polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; and polymethacrylate resin. When a resin other than the polycarbonate resin (A) is contained, the content thereof is preferably 45 parts by mass or less per 100 parts by mass of the polycarbonate resin (A), and particularly preferably 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, and particularly preferably 1 part by mass or less.

[0070] [Polycarbonate resin composition] The polycarbonate resin composition of the present invention can be molded into a molded article. The molding method for producing a molded article can be any molding method commonly used for polycarbonate resin compositions. Examples include injection molding, ultra-high speed injection molding, injection compression molding, two-color molding, gas-assisted hollow molding, molding using an insulated mold, molding using a rapidly heated mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding), extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, press molding, and blow molding. Molding methods using a hot runner system can also be used. Among these, injection molding methods such as injection molding, ultra-high speed injection molding, and injection compression molding are preferred.

[0071] [Molded products] Examples of molded articles include parts for electrical and electronic equipment, office automation equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods and miscellaneous goods, lighting equipment, etc. Among these, the molded articles are suitable for use in parts for electrical and electronic equipment, office automation equipment, information terminal equipment, home appliances, lighting equipment, etc., and are suitable for use in, for example, components for secondary battery devices used indoors or outdoors, battery packs, storage batteries for electric bicycles, etc., and components for housings used outdoors. [Example]

[0072] The present invention will be explained in more detail below by showing examples, but the present invention should not be construed as being limited to the following examples. The components used in the examples and comparative examples are as shown in Table 1 below.

[0073] [Table 1]

[0074] (Examples 1-1 to 4-1, Comparative Examples 1-1 to 4-1) <Production of Resin Composition Pellets> The above-mentioned components were blended in the ratios (parts by mass) shown in the table below and mixed in a tumbler for 20 minutes, and then fed to a twin-screw extruder "TEX30α" equipped with one vent, manufactured by The Japan Steel Works, Ltd., and kneaded under conditions of a screw rotation speed of 120 rpm, a discharge rate of 30 kg / hr, and a barrel temperature of 280°C. The molten resin extruded in the form of strands was quenched in a water tank and pelletized using a pelletizer to obtain pellets of a polycarbonate resin composition.

[0075] <Liquidity (Q value, unit: x 10 -2 cm 3 / sec)> The fluidity (flow value: Q value) of each polycarbonate resin composition was evaluated by drying the pellets obtained by the above-mentioned production method at 120°C for 4 hours, and then measuring the fluidity using a Shimadzu Corporation constant test force extrusion capillary rheometer "CFT-500D" under the conditions of a cylinder temperature of 280°C, a test force of 160 kgf, and a melting time of 7 minutes. The Q value measured under these conditions is referred to as "Q value" in the table below.

[0076] <Pressure Cooker (PCT) Test> The pellets obtained by the above manufacturing method were subjected to a moist heat treatment at 121°C, 100% RH, and 0.1 MPa using an ESPEC highly accelerated life tester "EHS-221M." After the moist heat treatment, the pellets were dried at 120°C for 4 hours and then measured using a Shimadzu constant test force extrusion capillary rheometer "CFT-500D" at a cylinder temperature of 280°C, a test force of 160 kgf, and a melting time of 7 minutes. The Q value measured under these conditions is referred to as "Q value (PCT)" in the table below.

[0077] The "humid heat Q value increase rate" was calculated using the following formula. Humid heat Q value increase rate (%) = [Q value (PCT) - Q value] ÷ [Q value] × 100 The rate of increase in the Q value under wet heat represents the rate of increase in fluidity due to resin deterioration under wet heat conditions, and a smaller value is preferred because it indicates better wet heat resistance.

[0078] <Thermal stability> The pellets obtained by the above-mentioned manufacturing method were dried at 120°C for 4 hours, and then the Q value was measured using a constant test force extrusion capillary rheometer "CFT-500D" manufactured by Shimadzu Corporation under the conditions of a cylinder temperature of 300°C, a test force of 160 kgf, and a melting time of 7 minutes. The Q value measured under these conditions is referred to as "300°C Q value" in the table below.

[0079] Furthermore, the pellets obtained by the above-mentioned manufacturing method were dried at 120°C for 4 hours, and then the Q value was measured using a constant test force extrusion capillary rheometer "CFT-500D" manufactured by Shimadzu Corporation under the conditions of a cylinder temperature of 300°C, a test force of 160 kgf, and a melting time of 17 minutes. The Q value measured under these conditions is referred to as "300°C Q value (retention)" in the table below.

[0080] The increase rate (%) of the retention Q value was calculated using the following formula. Retention Q value increase rate (%) = [300°C Q value (retention) - 300°C Q value] ÷ [300°C Q value] × 100 The rate of increase in the residence Q value represents the rate of increase in the fluidity of the resin due to residence heat deterioration, and a smaller value is preferred because it indicates superior residence heat stability.

[0081] The results are shown in Tables 2 to 5.

[0082] [Table 2]

[0083] [Table 3]

[0084] [Table 4]

[0085] [Table 5] [Industrial Applicability]

[0086] The polycarbonate resin composition of the present invention has high flame retardancy, and is also excellent in thermal stability, moist heat resistance and flowability, and can therefore be suitably used for various molded articles.

Claims

1. A polycarbonate resin composition comprising, per 100 parts by mass of polycarbonate resin (A), 0.01 to 0.5 parts by mass of an organic sulfonate metal salt (B), 0.001 to 0.08 parts by mass of an alicyclic epoxy compound (C), and 0 to 0.10 parts by mass of a phosphorus-based heat stabilizer, wherein the content ratio (C) / (B) of the organic sulfonate metal salt (B) to the alicyclic epoxy compound (C) is from 0 to less than 1.0, and the polycarbonate resin composition does not contain a silicone compound, or, if it contains a silicone compound, the amount of the silicone compound is less than 0.01 part by mass per 100 parts by mass of polycarbonate resin (A).

2. The polycarbonate resin composition according to claim 1, further comprising more than 0 part by mass and not more than 0.10 part by mass of a phosphorus-based heat stabilizer (D) per 100 parts by mass of the polycarbonate resin (A).

3. 3. Pellets of the polycarbonate resin composition according to claim 1 or 2.

4. A molded article obtained by molding the polycarbonate resin composition according to claim 1 or 2.

5. A molded article obtained by molding the polycarbonate resin pellets according to claim 3.

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