Polycarbonate resin composition

Abstract

To provide a polycarbonate resin composition that has very high flame retardancy, and also has excellent thermostability for thermal residence during molding.SOLUTION: A polycarbonate resin composition contains, relative to 100 pts.mass of polycarbonate resin (A), alkylbenzenesulfonic acid metal salt (B) of 0.001-0.5 pt.mass, and fluoropolymer (C) of 0.001-1 pt.mass. The alkylbenzenesulfonic acid metal salt (B) includes ortho forms of 5-100 mass%.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 extremely high flame retardancy and excellent thermal stability against retention during molding, and a molded article thereof. [Background technology]

[0002] Polycarbonate resin has excellent mechanical properties such as impact resistance, as well as excellent heat resistance and transparency, and is therefore widely used in a variety of applications, including electrical and electronic equipment parts, automotive interior and exterior parts, office automation equipment parts, various optical parts, machine parts, building materials, and sheets.

[0003] In recent years, high flame retardancy has been required for parts of electrical and electronic equipment, information terminal equipment, etc., and in particular, there is a growing demand for them to meet not only UL-94 V-0 but also a higher flame retardancy level of 5VB.

[0004] As a means for imparting flame retardancy to polycarbonate resins, halogen-based flame retardants have been conventionally used, but in recent years, phosphorus-based flame retardants and organic sulfonic acid metal salt-based flame retardants have come to be used. As an organic sulfonic acid metal salt-based flame retardant, for example, a compound in which SO3M (where M is an alkali metal or alkaline earth metal) is bonded to an aryl group of an aromatic ring, as described in Patent Document 1, is used. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 52-43100 Summary of the Invention [Problem to be solved by the invention]

[0006] Among aromatic sulfonate metal salts, alkylbenzene sulfonate metal salts exhibit excellent flame retardancy and are widely used. However, they are not sufficient to achieve 5VB-level flame retardancy (all five test pieces burn within 60 seconds, and no cotton ignition due to dripping occurs). Furthermore, resin compositions are prone to thermal degradation during molding or when exposed to high temperatures such as 300°C. Therefore, excellent 5VB-level flame retardancy and thermal stability during heat retention and high-temperature molding are highly desirable. The present invention has been made in view of the above circumstances, and an object (object) of the present invention is to provide a polycarbonate resin composition that has extremely high flame retardancy and excellent thermal stability against retention during molding, etc. [Means for solving the problem]

[0007] As a result of extensive research conducted by the present inventors in order to achieve the above object, they found that a polycarbonate resin composition containing a metal salt of alkylbenzenesulfonate containing a specific amount of ortho-isomer and a fluoropolymer in specific amounts can solve the above object, and thus completed the present invention. The present invention relates to the following polycarbonate resin composition and molded article.

[0008] 1. A polycarbonate resin composition comprising 100 parts by mass of polycarbonate resin (A), 0.001 to 0.5 parts by mass of metal alkylbenzenesulfonate (B), and 0.001 to 1 part by mass of fluoropolymer (C), wherein the metal alkylbenzenesulfonate (B) contains 5 to 100% by mass of an ortho isomer. 2. The polycarbonate resin composition according to the above item 1, wherein the metal alkylbenzenesulfonate (B) contains 5% by mass or more and less than 100% by mass of the ortho-isomer. 3. The polycarbonate resin composition according to the above 1 or 2, wherein the metal alkylbenzenesulfonate (B) is a metal toluenesulfonate. 4. The polycarbonate resin composition according to any one of the above 1 to 3, wherein the metal alkylbenzenesulfonate (B) is an alkali metal salt. 5. The polycarbonate resin composition according to any one of the above 1 to 4, further comprising 0.01 to 10 parts by mass of an elastomer (D) per 100 parts by mass of the polycarbonate resin (A). 6. A molded article made from the polycarbonate resin composition according to any one of 1 to 5 above. [Effects of the Invention]

[0009] The polycarbonate resin composition of the present invention has high flame retardancy at the 5VB level, and also has excellent thermal stability during heat retention and high-temperature molding. 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 0.001 to 0.5 parts by mass of a metal alkylbenzenesulfonate (B) and 0.001 to 1 part by mass of a fluoropolymer (C) per 100 parts by mass of a polycarbonate resin (A), and the metal alkylbenzenesulfonate (B) contains 5 to 100% by mass of an ortho isomer.

[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, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid-phase transesterification of prepolymers. 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 using methylene chloride as a solvent at 25° C., 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 preferable to contain both virgin raw materials and recycled resin, or it may be made of recycled polycarbonate resin. The proportion of recycled polycarbonate resin in the polycarbonate resin (A) is preferably 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] [Alkylbenzenesulfonic acid metal salt (B)] The polycarbonate resin composition of the present invention contains a metal alkylbenzenesulfonate (B).

[0030] The metal constituting the metal salt is preferably an alkali metal or alkaline earth metal. Examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium. Examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. Preferred are alkali metals, more preferably sodium, potassium, and cesium, and particularly preferably sodium.

[0031] Examples of the alkyl group of the metal alkylbenzenesulfonate (B) include a methyl group, an ethyl group, a propyl group, a butyl group, etc., and are preferably a methyl group or an ethyl group, with a methyl group being particularly preferred. The alkyl substitution on the benzene ring may be a monoalkyl substitution or a dialkyl substitution, etc., but is preferably a monoalkyl substitution, and is preferably a monoalkylbenzenesulfonate metal salt, and examples thereof include the ortho-, para-, and meta-isomers thereof. As the metal alkylbenzenesulfonate (B), metal o-toluenesulfonate, metal p-toluenesulfonate, and metal m-toluenesulfonate are preferred, and sodium and potassium salts thereof are more preferred.

[0032] In the present invention, the metal alkylbenzenesulfonate (B) contains 5 to 100% by mass of the ortho-isomer. The amount of the ortho-isomer metal alkylbenzenesulfonate in the metal alkylbenzenesulfonate (B) is preferably 5% by mass or more but less than 100% by mass, more preferably 8% by mass or more, even more preferably 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, and particularly preferably 50% by mass or more, and even more preferably 95% by mass or less, even more preferably 90% by mass or less or 85% by mass or less, even more preferably 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, and particularly preferably 60% by mass or less. By using the metal alkylbenzenesulfonate (B) containing the ortho isomer in the above proportion, it is possible to obtain a polycarbonate resin composition that has high flame retardancy at the 5VB level and also has excellent thermal stability during heat retention and high-temperature molding.

[0033] The content of the alkylbenzenesulfonic acid metal salt (B) is 0.001 to 0.5 parts by mass per 100 parts by mass of the polycarbonate resin (A). A resin composition containing such an amount has high flame retardancy and excellent thermal stability during heat retention and high-temperature molding. The content of the alkylbenzenesulfonic acid metal salt (B) is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, 0.04 part by mass or more, particularly preferably 0.05 part by mass or more, and also preferably 0.4 part by mass or less, more preferably 0.3 part by mass or less, 0.2 part by mass or less, 0.15 part by mass or less, particularly preferably 0.1 part by mass or less.

[0034] [Fluoropolymer (C)] The polycarbonate resin composition of the present invention contains the fluoropolymer (C) in an amount of 0.001 to 1 part by mass per 100 parts by mass of the polycarbonate resin (A). The fluoropolymer may be used alone or in any combination of two or more in any ratio. By including the fluoropolymer in this way, the melting properties of the resin composition can be improved, and the ability to prevent dripping during combustion can be improved. If the content of the fluoropolymer (C) is less than 0.001 part by mass, the effect of improving flame retardancy becomes insufficient, and if it exceeds 1 part by mass, the molded article obtained by molding the resin composition will have poor appearance and reduced mechanical strength. The content of the fluoropolymer (C) is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, even more preferably 0.15 part by mass or more, particularly preferably 0.2 part by mass or more, and is preferably 0.8 part by mass or less, more preferably 0.6 part by mass or less, particularly preferably 0.5 part by mass or less, per 100 parts by mass of the polycarbonate resin (A).

[0035] The fluoropolymer (C) is preferably a fluoroolefin resin. Fluoroolefin resins are usually polymers or copolymers containing a fluoroethylene structure, and specific examples include difluoroethylene resins, tetrafluoroethylene resins, and tetrafluoroethylene / hexafluoropropylene copolymer resins, with tetrafluoroethylene resins being particularly preferred. The fluoropolymer is preferably one having fibril-forming ability, specifically, a fluoroolefin resin having fibril-forming ability. By having fibril-forming ability, the drip prevention property during combustion tends to be significantly improved.

[0036] The fluoroolefin resin having fibril-forming ability is preferably a fluoroethylene resin having fibril-forming ability, and examples thereof include "Teflon (registered trademark) 6J" manufactured by Mitsui-Chemours Fluoroproducts, Inc., and "Polyflon F201L," "Polyflon F103," and "Polyflon FA500C" manufactured by Daikin Chemical Industries, Ltd. Furthermore, examples of commercially available aqueous dispersions of fluoroethylene resins include "Teflon (registered trademark) 30J" and "Teflon (registered trademark) 31-JR" manufactured by Mitsui-Chemours Fluoroproducts, Inc., and "Fluon D-1" manufactured by Daikin Chemical Industries, Ltd. Furthermore, fluoroethylene polymers having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such fluoroethylene polymers include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene composites, polymethyl methacrylate-fluoroethylene composites, and polybutyl methacrylate-fluoroethylene composites, such as "Metablen A-3800" manufactured by Mitsubishi Chemical Corporation and "Brendex 449" manufactured by GE Specialty Chemicals.

[0037] The fluoropolymer (C) may be contained either as one type or as two or more types in any combination and ratio.

[0038] [Elastomer (D)] The polycarbonate resin composition of the present invention also preferably contains an elastomer (D). The elastomer (D) is preferably a graft rubber copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. Such a graft rubber copolymer may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and the copolymerization method may be either single-stage grafting or multi-stage grafting.

[0039] The rubber component typically has a glass transition temperature of 0°C or lower, preferably -20°C or lower, and more preferably -30°C or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polyalkyl acrylate rubbers such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymers, silicone rubbers such as organopolysiloxane rubber, butadiene-acrylic composite rubbers, IPN composite rubbers consisting of organopolysiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-α-olefin rubbers such as ethylene-propylene rubber, ethylene-butene rubber, and ethylene-octene rubber, ethylene-acrylic rubber, and fluororubber. These may be used alone or in combination. Among these, polybutadiene rubber, polyalkyl acrylate rubber, IPN type composite rubber consisting of organopolysiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferred in terms of mechanical properties and surface appearance.

[0040] Specific examples of the monomer component graft-copolymerizable with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides (e.g., maleic anhydride). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, and (meth)acrylic acid compounds are preferred in terms of mechanical properties and surface appearance, and (meth)acrylic acid ester compounds are more preferred. Specific examples of (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate.

[0041] From the viewpoints of impact resistance and surface appearance, the elastomer (D) is preferably a core / shell graft copolymer. Among these, a core / shell graft copolymer is preferred, which has a core layer made of at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, and an IPN-type composite rubber composed of organopolysiloxane rubber and polyalkyl acrylate rubber, and a shell layer formed by copolymerizing a (meth)acrylic acid ester around the core. A core / shell elastomer having a butadiene-based rubber core is particularly preferred. The core / shell graft copolymer preferably contains 40% by mass or more of the rubber component, more preferably 60% by mass or more. Furthermore, the (meth)acrylic acid component is preferably 10% by mass or more.

[0042] Preferred specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer, methyl methacrylate-(acrylic-silicone IPN rubber) copolymer, etc. Such rubbery polymers may be used alone or in combination of two or more.

[0043] When the polycarbonate resin composition of the present invention contains the elastomer (D), it preferably contains the elastomer (D) in an amount of 0.01 to 10 parts by mass, particularly 1 to 10 parts by mass, and especially 2 to 8 parts by mass per 100 parts by mass of the polycarbonate resin (A).

[0044] [Stabilizer] 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.

[0045] 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 2B 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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 phenolic 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.

[0050] The content of the phenolic stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A). By setting the content of the phenolic stabilizer to the lower limit of the above range or more, the effect as a phenolic stabilizer can be sufficiently obtained. Furthermore, by setting the content of the phenolic stabilizer to the upper limit of the above range or less, the effect does not plateau, which is economical.

[0051] [UV absorber] The polycarbonate resin composition of the present invention also preferably contains an ultraviolet absorber. Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; and organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, and hindered amine compounds. Among these, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred. By selecting an organic ultraviolet absorber, the transparency and mechanical properties of the resin composition of the present invention can be improved.

[0052] Specific examples of the benzotriazole compound include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzotriazole. t-amyl)-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], etc., among which 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] are preferred, and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole is particularly preferred.

[0053] Specific examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0054] Specific examples of the salicylate compound include phenyl salicylate, 4-tert-butylphenyl salicylate, and the like. Specific examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and the like. Specific examples of oxanilide compounds include 2-ethoxy-2'-ethyloxalinic acid bis-alinide. As the malonic acid ester compound, 2-(alkylidene)malonic acid esters are preferred, and 2-(1-arylalkylidene)malonic acid esters are more preferred.

[0055] When an ultraviolet absorber is contained, its content is usually 0.05 parts by mass or more, preferably 0.1 parts 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). If the content of the ultraviolet absorber is less than the lower limit of the above range, the effect of improving weather resistance and light resistance may be insufficient, whereas if the content of the ultraviolet absorber exceeds the upper limit of the above range, mold deposits or the like may occur, causing mold contamination. The ultraviolet absorber may be contained alone or in any combination and ratio of two or more kinds.

[0056] [Release agent] The polycarbonate resin composition of the present invention preferably contains a mold release agent (lubricant). Examples of the mold release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, and polysiloxane-based silicone oils.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] Examples of polysiloxane-based silicone oils include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

[0063] The above-mentioned release agents may be contained either alone or in any combination and ratio of two or more.

[0064] The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass or less, relative to 100 parts by mass of the polycarbonate resin (A). By setting the content of the release agent to be equal to or more than the lower limit of the above range, it becomes easier to obtain a sufficient effect of mold releasability, and by setting the content of the release agent to be equal to or less than the upper limit of the above range, it becomes less likely that mold contamination will occur during injection molding.

[0065] [Additives, etc.] The polycarbonate resin composition of the present invention may contain additives other than those described above, such as flame retardants other than the metal alkylbenzenesulfonate (B), fluorescent brighteners, pigments, dyes, plasticizers, compatibilizers, etc. These additives may be contained alone or in combination of two or more.

[0066] Furthermore, the polycarbonate resin (A) may contain other resins. 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), and acrylonitrile-styrene copolymer (AS 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 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, per 100 parts by mass of the polycarbonate resin (A).

[0067] [Polycarbonate resin composition] The polycarbonate resin composition of the present invention has high flame retardancy and is inhibited from dripping during the UL-94 5V test, eliminating dripping, making it possible to achieve 5VB on a 3.0 mm thick UL test piece.

[0068] The polycarbonate resin composition is 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.

[0069] [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]

[0070] In order to confirm the effects of the polycarbonate resin composition of the present invention, polycarbonate resin compositions were produced as follows and various evaluations were carried out, but the present invention should not be construed as being limited to the following examples. The ingredients used are as shown in Table 1 below.

[0071] [Table 1]

[0072] (Examples 1 to 11, Comparative Examples 1 to 3 <Production of Resin Composition Pellets> The above-mentioned components were blended in the proportions (parts by mass) shown in Table 4 below, mixed in a tumbler for 20 minutes, and then fed to a twin-screw extruder "TEX30αII" 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.

[0073] <Preparation of test specimens> The pellets obtained by the above-mentioned manufacturing method were dried at 120°C for 4 hours, and then injection-molded using an SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. under conditions of a cylinder temperature of 260°C, a mold temperature of 80°C, and a molding cycle of 30 seconds to obtain test pieces for UL flammability testing measuring 125 mm in length, 13 mm in width, and 3.0 mm in thickness.

[0074] <Flammability evaluation> The flammability of each polycarbonate resin composition was evaluated by conditioning the test specimens for UL combustion tests obtained by the above method in a thermo-hygrostat chamber at a temperature of 23°C and a humidity of 50% for 48 hours, and conducting the test in accordance with the UL94 test (combustion test for plastic materials for parts of equipment) defined by UL in the United States.

[0075] <UL94-V test> In the UL94-V test, the flammability is evaluated from the afterglow time and dripping property after applying the flame of a burner to the lower end of a vertically held test specimen of a predetermined size for 10 seconds. In order to have a flammability of V-0, V-1, and V-2, it is necessary to meet the criteria shown in Table 2 below.

[0076]

Table 2

[0077] Here, the afterglow time is the length of time during which the flaming combustion of the test specimen continues after the ignition source is removed. Also, ignition of cotton by dripping is determined by whether the cotton for marking, which is approximately 300 mm below the lower end of the test specimen, is ignited by the dripping (drip) material from the test specimen. Furthermore, if even one of the five tests for one material does not meet the above criteria, it is evaluated as NR (not rated) as not satisfying V-2.

[0078] <ul94-5vb> In the UL94-5V test, flame resistance is evaluated based on the afterflame time and dripping properties after a burner flame is applied to the corner of a bar test piece of a specified size, which is held vertically and tilted 20 degrees from the vertical, for 5 seconds, and then removed for 5 seconds. This cycle is repeated five times. In order to have 5VB flame resistance, the material must meet the standards shown in Table 3 below.

[0079] [Table 3]

[0080] Here, the afterflame time is the length of time the test specimen continues to burn with a flame after the fifth contact with the flame. Cotton ignition by dripping is determined by whether or not the cotton marking, located approximately 300 mm below the bottom of the test specimen, is ignited by dripping material from the test specimen. Furthermore, if even one of the five tests for a single material did not meet the above criteria, it was rated as NR (not rated).

[0081] [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 them using a constant test force extrusion capillary rheometer "CFT-500D" manufactured by Shimadzu Corporation under 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 (280°C, no retention)" in the tables below.

[0082] [Retention 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 Shimadzu 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 17 minutes. The Q value measured under these conditions is referred to as "Q value (280°C, 10 minute residence time)" in the table below. The increase rate (%) of the retention Q value was calculated using the following formula. Retention Q value increase rate (%) = [Q value (280°C, 10 min. dwell) - Q value (280°C, no dwell)] ÷ [Q value (280°C, no dwell)] × 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.

[0083] [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 Shimadzu constant test force extrusion capillary rheometer "CFT-500D" 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 "Q value (300°C, no retention)" in the table below. The temperature Q value increase rate (%) was calculated using the following formula. Temperature Q value increase rate (%) = [Q value (300°C, no retention) - Q value (280°C, no retention)] ÷ [Q value (280°C, no retention)] × 100 The temperature Q value increase rate represents the rate at which the fluidity of a resin increases due to thermal degradation during high-temperature molding. A smaller value is preferred because it indicates superior thermal stability and allows the physical properties to be maintained even during high-temperature molding.

[0084] The evaluation results are shown in Table 4 below. In the table, "Actual" indicates an example, and "Comparative" indicates a comparative example.

[0085] [Table 4] [Industrial Applicability]

[0086] The polycarbonate resin composition of the present invention has an extremely high level of flame retardancy and is excellent in thermal stability against retention during molding, and therefore can be suitably used for various molded articles.

Claims

1. A polycarbonate resin composition comprising 0.001 to 0.5 parts by mass of a metal alkylbenzenesulfonate (B) and 0.001 to 1 part by mass of a fluoropolymer (C) per 100 parts by mass of a polycarbonate resin (A), wherein the metal alkylbenzenesulfonate (B) contains 5 to 100% by mass of an ortho isomer.

2. 2. The polycarbonate resin composition according to claim 1, wherein the metal alkylbenzenesulfonate (B) contains 5% by mass or more and less than 100% by mass of an ortho-isomer.

3. 3. The polycarbonate resin composition according to claim 1, wherein the metal alkylbenzenesulfonate (B) is a metal toluenesulfonate.

4. 4. The polycarbonate resin composition according to claim 1, wherein the metal alkylbenzenesulfonate (B) is an alkali metal salt.

5. 5. The polycarbonate resin composition according to claim 1, further comprising 0.01 to 10 parts by mass of an elastomer (D) per 100 parts by mass of the polycarbonate resin (A).

6. A molded article made from the polycarbonate resin composition according to any one of claims 1 to 5.

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