Flame-retardant polycarbonate resin composition

Abstract

To provide a flame-retardant polycarbonate resin composition which clears PFBS regulation, can comply with PFAS regulation, and has excellent flame retardancy.SOLUTION: A flame-retardant polycarbonate resin composition is provided, containing with respect to 100 pts.mass of (A) an aromatic polycarbonate resin, 0.05-0.3 pts.mass of (B) an organic sulfonic acid-based flame retardant containing no fluorine, (C) no polytetrafluoroethylene or 0.09 pts.mass or less of the polytetrafluoroethylene, wherein in the resin composition, amounts of a perfluorobutane sulfonic acid and its metal salt (PFBS) are less than 10 ppm, an amount of a polyfluoroalkyl compound (PFAS) is less than 1,000 ppm, and (A) the aromatic polycarbonate resin is composed of 50-100 mass% of an aromatic polycarbonate resin (A1) having a degree (Mw / Mn) of dispersion of 3.0 or more, and 50-0 mass% of an aromatic polycarbonate resin (A2) having a degree (Mw / Mn) of dispersion of less than 3.0.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a flame-retardant polycarbonate resin composition, and more particularly, to a flame-retardant polycarbonate resin composition having excellent flame retardancy that clears PFBS regulations and also meets PFAS regulations.

Background Art

[0002] Polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical properties, and is widely used as a material for manufacturing parts in, for example, vehicle parts, electrical and electronic equipment parts, housing members, and other industrial fields. In particular, flame-retardant polycarbonate resin compositions are suitably used as parts for vehicle parts, electrical and electronic equipment parts such as personal computers, mobile phones, battery cases, and OA and information equipment such as printers and copiers.

[0003] As a means for imparting flame retardancy to polycarbonate resin, halogen-based flame retardants have been conventionally used, and in recent years, phosphorus-based flame retardants and organic sulfonic acid metal salt-based flame retardants have been used. Such flame retardants can suppress dripping and improve flame retardancy by being blended with polyfluoroethylene as a dripping inhibitor, and the present applicant has also made various proposals. For example, in Patent Document 1, a flame-retardant polycarbonate resin composition containing a specific core-shell type graft copolymer having a butadiene-based rubber as a core, a fluorinated polyolefin, and an organic sulfonic acid metal salt-based flame retardant, specifically potassium perfluorobutane sulfonate, in an aromatic polycarbonate resin was proposed.

[0004] However, in recent years, fluorine compounds have become subject to international regulations, primarily in Japan, Europe, and the United States, and there are moves to further strengthen these regulations. In the EU, perfluorobutanesulfonic acid and its metal salts (PFBS) are regulated under REACH, and it is predicted that these regulations will be strengthened and banned in a few years. Furthermore, PFAS regulations for perfluoro and polyfluoroalkyl compounds are progressing, mainly in the EU and the United States, and although currently focused on specific sectors such as food and textiles, there is a possibility that these regulations will spread to other sectors. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2019-19191 [Overview of the project] [Problems that the invention aims to solve]

[0006] Therefore, in order to comply with the aforementioned PFBS and PFAS regulations, there is a strong demand for polycarbonate resin compositions that exhibit excellent flame retardancy without relying on metal perfluorobutanesulfonic acid salts or polytetrafluoroethylene. However, polytetrafluoroethylene is an effective drip inhibitor, and achieving V-0 in the UL-94 test without it is not easy. This invention has been made in view of the above circumstances, and its objective (problem) is to provide a flame-retardant polycarbonate resin composition that meets the requirements of PFBS regulations and complies with PFAS regulations, while exhibiting excellent flame retardancy. [Means for solving the problem]

[0007] The inventors of the present invention have conducted extensive research to achieve the above objectives and have found that the above objectives can be solved by combining an aromatic polycarbonate resin consisting of 50 to 100% by mass of an aromatic polycarbonate resin with a dispersion degree (Mw / Mn) of 3.0 or higher and 50 to 0% by mass of an aromatic polycarbonate resin with a dispersion degree (Mw / Mn) of less than 3.0 with a non-fluorine-based organic sulfonic acid-based flame retardant composition. This led to the completion of the present invention. This invention relates to the following flame-retardant polycarbonate resin compositions and molded articles.

[0008] [1] (A) Aromatic polycarbonate resin, per 100 parts by mass, (B) containing 0.05 to 0.3 parts by mass of an organic sulfonic acid-based flame retardant that does not contain fluorine, and (C) not containing polytetrafluoroethylene, or if it is contained, the amount is 0.09 parts by mass or less. A resin composition in which the amount of perfluorobutanesulfonic acid and its metal salt (PFBS) is less than 10 ppm and the amount of polyfluoroalkyl compound (PFAS) is less than 1000 ppm, (A) A flame-retardant polycarbonate resin composition characterized by comprising 50 to 100% by mass of aromatic polycarbonate resin (A1) having a dispersion degree (Mw / Mn) of 3.0 or higher as measured by GPC, and 50 to 0% by mass of aromatic polycarbonate resin (A2) having a dispersion degree (Mw / Mn) of less than 3.0 as measured by GPC. [2](B) The flame-retardant polycarbonate resin composition according to [1] above, wherein the organic sulfonic acid-based flame retardant is one or more of the following: p-toluenesulfonic acid or its metal salt, phenylsulfonylbenzenesulfonic acid or its metal salt, or polystyrenesulfonic acid or its metal salt. [3] A molded article of the flame-retardant polycarbonate resin composition described in [1] or [2] above. [Effects of the Invention]

[0009] The flame-retardant polycarbonate resin composition of the present invention complies with PFBS regulations and PFAS regulations, exhibits excellent flame retardancy, and also has excellent moldability. Sagging during combustion is a phenomenon that occurs under extremely low shear conditions, and having a component with a large molecular weight in the polycarbonate resin increases the melt viscosity and suppresses sagging. On the other hand, when injection molding, it is necessary to obtain fluidity under high shear conditions, so a component with a small molecular weight is preferable, and the two are in a trade-off relationship. In the present invention, the above points are resolved by including 50% by mass or more of a highly dispersed aromatic polycarbonate resin (A1) with a dispersion degree (Mw / Mn) of 3.0 or higher as a single component. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below with reference to embodiments and examples. In this specification, unless otherwise specified, "~" means that the numbers before and after it are included as the lower and upper limits.

[0011] The flame-retardant polycarbonate resin composition of the present invention contains (A) 0.05 to 0.3 parts by mass of (B) an organic sulfonic acid-based flame retardant that does not contain fluorine, per 100 parts by mass of aromatic polycarbonate resin, and (C) no polytetrafluoroethylene, or if it is contained, its content is 0.09 parts by mass or less. A resin composition in which the amount of perfluorobutanesulfonic acid and its metal salt (PFBS) is less than 10 ppm and the amount of polyfluoroalkyl compound (PFAS) is less than 1000 ppm, (A) The aromatic polycarbonate resin is characterized by comprising 50 to 100% by mass of aromatic polycarbonate resin (A1) with a dispersion degree (Mw / Mn) of 3.0 or higher as measured by GPC, and 50 to 0% by mass of aromatic polycarbonate resin (A2) with a dispersion degree (Mw / Mn) of less than 3.0 as measured by GPC. The present invention will be described in detail below.

[0012] [(A) Aromatic polycarbonate resin] The aromatic polycarbonate resin (A) used in the present invention consists of 50 to 100% by mass of aromatic polycarbonate resin (A1) with a dispersion degree (Mw / Mn) of 3.0 or higher as measured by GPC, and 50 to 0% by mass of aromatic polycarbonate resin (A2) with a dispersion degree (Mw / Mn) of less than 3.0 as measured by GPC.

[0013] The aromatic polycarbonate resins (A1) and (A2) are aromatic polycarbonate polymers obtained by reacting an aromatic dihydroxy compound with a phosgene or carbonic acid diester. The method for producing the aromatic polycarbonate resins (A1) and (A2) is not particularly limited and can be done by conventional methods such as the phosgene method (interfacial polymerization method) or the melting method (transesterification method).

[0014] Representative aromatic dihydroxy compounds include, for example, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ether, and bis(4-hydroxyphenyl)ketone.

[0015] Among the aromatic dihydroxy compounds mentioned above, those starting from 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) or 2,2-bis(4-hydroxy-3-methylphenyl)propane (i.e., bisphenol C) are preferred, and those starting from bisphenol A are particularly preferred. In addition, the above aromatic dihydroxy compound may be used alone or in combination of two or more kinds.

[0016] <Aromatic polycarbonate resin (A1)> The aromatic polycarbonate resin (A1) is an aromatic polycarbonate resin having a dispersity (Mw / Mn) of 3.0 or more measured by GPC. In the present invention, by containing 50% by mass or more of the highly dispersed aromatic polycarbonate resin (A1) having a dispersity (Mw / Mn) of 3.0 or more as a single substance in the (A) aromatic polycarbonate resin, it is possible to achieve both prevention of sagging and moldability in injection molding and the like.

[0017] The aromatic polycarbonate resin (A1) may be used alone or in combination with an aromatic polycarbonate resin (A1) having a dispersity (Mw / Mn) of 3.0 or more.

[0018] As a method for adjusting Mw / Mn of the aromatic polycarbonate resin (A1), a conventionally known method can be adopted and is not particularly limited. For example, the amount of the molecular weight regulator used in the polymerization step can be adjusted, the addition time of the molecular weight regulator can be changed, or the polymerization conditions such as the reaction time and reaction temperature can be adjusted. Aromatic polycarbonate resins having a dispersity (Mw / Mn) of 3.0 or more are also commercially available, and it is also possible to appropriately select these and use them as the aromatic polycarbonate resin (A1).

[0019] The upper limit of Mw / Mn of the aromatic polycarbonate resin (A1) is preferably 5 or less, more preferably 4 or less, particularly preferably 3.7 or less, and especially preferably 3.5 or less.

[0020] The Mw of the aromatic polycarbonate resin (A1) is preferably 40,000 or more, more preferably 50,000 or more. The Mn is preferably 15,000 or more, more preferably 17,000 or more.

[0021] In this invention, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polycarbonate resin are values ​​obtained by converting them to polystyrene equivalents using gel permeation chromatography (GPC). The GPC measurements were performed specifically as follows: A gel permeation chromatography system, specifically an HLC-8320GPC / EcoSEC (manufactured by Tosoh Corporation), was used, with three KF-805L columns and one KF-800D column (both manufactured by Shodex). The column temperature was set to 40°C. The HLC-8320's built-in radioisotope detector was used. Tetrahydrofuran was used as the eluent, and a calibration curve was created using standard polystyrene (manufactured by Agilent).

[0022] The molecular weight of the aromatic polycarbonate resin (A1) is the viscosity-average molecular weight (Mv) calculated from the solution viscosity measured at 25°C using methylene chloride as the solvent, preferably 13,000 or more, more preferably 18,000 or more, particularly 20,000 or more, preferably 40,000 or less, and particularly preferably 33,000 or less.

[0023] The viscosity-average molecular weight [Mv] of polycarbonate resin is calculated by determining the intrinsic viscosity [η] (unit: dl / g) at 25°C using a Ubbelohde viscometer with methylene chloride as the solvent, and then using Schnell's viscosity formula, i.e., η = 1.23 × 10⁻¹⁰. -4 Mv 0.83 It refers to the value calculated from [the formula]. In addition, intrinsic viscosity [η] is the specific viscosity [η] at each solution concentration [C] (g / dl). sp This value was calculated by measuring [the value] and using the following formula.

number

[0024] <Aromatic polycarbonate resin (A2)> Aromatic polycarbonate resin (A2) is an aromatic polycarbonate resin whose dispersion (Mw / Mn) measured by GPC is less than 3.0.

[0025] The aromatic polycarbonate resin (A2) has the same raw material components and polymerization method as described for aromatic polycarbonate resin (A1). Aromatic polycarbonate resin (A2) is preferably an aromatic polycarbonate resin, more preferably one starting from bisphenol A or bisphenol C, and particularly preferably one starting from bisphenol A.

[0026] The content of aromatic polycarbonate resin (A2) is 50 to 0% by mass in aromatic polycarbonate resin (A), and aromatic polycarbonate resin (A1) is 50 to 100% by mass, preferably 55 to 100% by mass of aromatic polycarbonate resin (A1) and 45 to 0% by mass of aromatic polycarbonate resin (A2), more preferably 60 to 100% by mass of (A1) and 40 to 0% by mass of (A2), and even more preferably 65 to 100% by mass of (A1) and 35 to 0% by mass of (A2). It is also preferable that (A1) be 50 to 95% by mass and (A2) be 50 to 5% by mass, and more preferably 50 to 90% by mass of (A1) and 50 to 10% by mass of (A2).

[0027] The Mw / Mn ratio of the aromatic polycarbonate resin (A2) is less than 3.0. The lower limit of Mw / Mn is preferably 2.2 or higher, more preferably 2.3 or higher, and the upper limit is preferably 2.9 or lower, more preferably 2.8 or lower.

[0028] The Mw of the aromatic polycarbonate resin (A2) is preferably 25,000 or more, and particularly preferably 30,000 or more. The Mn is preferably 10,000 or more, and even more preferably 15,000 or more.

[0029] Methods for adjusting the Mw / Mn of aromatic polycarbonate resin (A2) can be conventionally known and are not particularly limited. Examples include adjusting the amount of molecular weight modifier used in the polymerization process, changing the timing of addition of the molecular weight modifier, adjusting polymerization conditions such as reaction time and reaction temperature, or supplying pellets or powder of aromatic polycarbonate resin to a poor solvent such as acetone to extract and remove low molecular weight components from the aromatic polycarbonate resin. Alternatively, a solution can be prepared by dissolving aromatic polycarbonate in a good solvent such as methylene chloride, and this solution can be supplied to a poor solvent such as acetone to precipitate the aromatic polycarbonate resin from which low molecular weight components have been reduced or removed. Aromatic polycarbonate resins with a dispersion degree (Mw / Mn) of less than 3.0 are also commercially available, and it is possible to select one of these as appropriate and use it as aromatic polycarbonate resin (A2).

[0030] The molecular weight of the aromatic polycarbonate resin (A2) is the viscosity-average molecular weight (Mv) calculated from the solution viscosity measured at 25°C using methylene chloride as the solvent, and is preferably 15,000 or more, more preferably 18,000 or more. It is also preferably 40,000 or less, and more preferably 30,000 or less.

[0031] Furthermore, the aromatic polycarbonate resins (A1) and (A2) may be not only virgin resins, but also polycarbonate resins recycled from used products (so-called material-recycled polycarbonate resins), or polycarbonate resins manufactured from polycarbonate resins that have been chemically decomposed and returned to their raw materials (so-called chemical-recycled polycarbonate resins). It is also preferable to contain both virgin resins and recycled resins, and it may consist solely of recycled polycarbonate resins.

[0032] (A) The degree of dispersion (Mw / Mn) of the aromatic polycarbonate resin as a whole is preferably 3.0 or higher, more preferably greater than 3.0, and even more preferably 3.05 or higher. The upper limit is preferably 3.6 or lower, more preferably 3.5 or lower, 3.45 or lower, and especially preferably 3.4 or lower.

[0033] [(B) Fluorine-free organosulfonic acid-based flame retardants] The flame-retardant polycarbonate resin composition of the present invention contains (B) a fluorine-free organic sulfonic acid flame retardant. The content of (B) the fluorine-free organic sulfonic acid flame retardant is 0.05 to 0.3 parts by mass, preferably 0.05 to 0.25 parts by mass, and more preferably 0.05 to 0.2 parts by mass, per 100 parts by mass of (A) aromatic polycarbonate resin. By combining (A) aromatic polycarbonate resin in such amounts, a flame-retardant polycarbonate resin composition that complies with PFBS and PFAS regulations and exhibits excellent flame retardancy can be obtained.

[0034] (B) As for fluorine-free organic sulfonic acid-based flame retardants, non-fluorine organic sulfonic acids or their metal salts that do not have CF bonds in their molecules are preferred.

[0035] The metal in the metal salt is preferably an alkali metal or an alkaline earth metal, such as alkali metals like lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); and alkaline earth metals like magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Among these, sodium, potassium, and cesium are preferred, with sodium and potassium being particularly preferred.

[0036] Preferred non-fluorinated organic sulfonic acids or their metal salts include aromatic sulfonic acids or their metal salts, aromatic sulfonamides (or sulfonimides) or their metal salts, and polystyrene sulfonic acids or their metal salts, and more preferably, these metal salts.

[0037] Specific examples of these include alkali metal salts of aromatic sulfonic acids having at least one aromatic group in their molecule, such as potassium 3-(phenylsulfonyl)benzenesulfonate (i.e., potassium diphenylsulfon-3-sulfonate), dipotassium diphenylsulfon-3,3'-disulfonate, sodium benzenesulfonate, potassium benzenesulfonate, cesium benzenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, cesium p-toluenesulfonate, 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 their molecule, such as magnesium p-toluenesulfonate, calcium p-toluenesulfonate, strontium p-toluenesulfonate, barium p-toluenesulfonate, magnesium dodecylbenzenesulfonate, and calcium dodecylbenzenesulfonate.

[0038] Examples of metal salts of aromatic sulfonamides (or sulfonimides) include potassium salt of N-(p-tolylsulfonyl)-p-toluenesulfoimide, potassium salt of N-(N'-benzylaminocarbonyl)sulfanilimide, and potassium salt of N-(phenylcarboxyl)-sulfanilimide.

[0039] (B) Among the above, p-toluenesulfonic acid-based flame retardants that do not contain fluorine are preferred, p-toluenesulfonic acid or its metal salt, phenylsulfonylbenzenesulfonic acid or its metal salt, and polystyrenesulfonic acid or its metal salt, and among these metal salts, alkali metal salts are particularly preferred.

[0040] (B) Fluorine-free organic sulfonic acid flame retardants may be used individually or in combination of two or more types in any combination and ratio.

[0041] [(C) Polytetrafluoroethylene] The flame-retardant polycarbonate resin composition of the present invention either does not contain (C) polytetrafluoroethylene, or if it does contain it, the amount is 0.09 parts by mass or less per 100 parts by mass of (A) aromatic polycarbonate resin. Polytetrafluoroethylene having fibril-forming ability has been used as a sagging prevention agent, but in the present invention, by either not containing (C) polytetrafluoroethylene, or if it does contain it, the amount is 0.09 parts by mass or less as described above, a flame-retardant polycarbonate resin composition that can comply with PFAS regulations can be made.

[0042] [Other resin components] The flame-retardant polycarbonate resin composition of the present invention may contain (A) fluorine-free resins other than aromatic polycarbonate resins, to the extent that the effects of the present invention are not impaired. Examples include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate resin, and polybutylene terephthalate resin; styrene-based resins such as polystyrene resin, high-impact polystyrene resin (HIPS), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES 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; and polysulfone resin. Note that other resins may be present individually, or two or more in any combination and ratio. If other resins are included, it is preferable that the amount is 30 parts by mass or less per 100 parts by mass of (A) aromatic polycarbonate resin, and more preferably 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 7 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, and especially 1 part by mass or less.

[0043] [Other additives] The flame-retardant polycarbonate resin composition of the present invention may further contain additives other than those described above, as long as they do not impair the effects of the present invention. Examples of such additives include stabilizers, mold release agents, ultraviolet absorbers, antistatic agents, dyes and pigments, antifogging agents, lubricants, antiblocking agents, sliding modifiers, impact resistance modifiers, plasticizers, dispersants, and antibacterial agents. These additives must not contain fluorine.

[0044] [Stabilizer] The flame-retardant polycarbonate resin composition of the present invention may also preferably contain a stabilizer, and phosphorus-based stabilizers or phenol-based stabilizers are preferred.

[0045] Any known phosphorus-based stabilizer can be used. Specific examples include phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphate, and other phosphorus oxoacids; acidic pyrophosphate metal salts such as sodium acidic pyrophosphate, potassium acidic pyrophosphate, and calcium acidic pyrophosphate; phosphates of Group 1 or Group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; and organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds, with organic phosphite compounds and organic phosphate 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, for example, "ADEKA Stab 1178," "ADEKA Stab 2112," and "ADEKA Stab HP-10" from ADEKA Corporation, "JP-351," "JP-360," and "JP-3CP" from Johoku Chemical Industry Co., Ltd., and "Irgaphos 168" from BASF.

[0047] Suitable organic phosphate compounds include metal salts of organic phosphates. Specifically, examples include mixtures of zinc salts of distearyl acid phosphate and zinc salts of monostearyl acid phosphate, monostearyl acid phosphates, and distearyl acid phosphates. Examples of such organic phosphate metal salts include "JP-518Zn" manufactured by Johoku Chemical Industry Co., Ltd. and "AX-71" manufactured by ADEKA Corporation.

[0048] Furthermore, the phosphorus-based stabilizer may be present in any combination and ratio, or in any combination of two or more types.

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

[0050] Examples of phenolic stabilizers include hindered phenolic antioxidants. Specific examples 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]phosphoate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6- Examples include triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[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-triazine-2-ylamino)phenol, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate.

[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. Examples of such phenolic antioxidants include BASF's "Irganox 1010" and "Irganox 1076," and ADEKA's "ADEKA Stab AO-50" and "ADEKA Stab AO-60." Furthermore, the phenolic stabilizer may be present in any combination and ratio, or in any combination of two or more types.

[0052] 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 (A) aromatic polycarbonate resin. If the content of the phenolic stabilizer is below the lower limit of the above range, the effect of the phenolic stabilizer may be insufficient, and if the content of the phenolic stabilizer exceeds the upper limit of the above range, the effect may plateau and become uneconomical.

[0053] [Release agent] The flame-retardant polycarbonate resin composition of the present invention preferably contains a mold release agent. While known mold release agents commonly used for resins can be used, polyolefin compounds and fatty acid ester compounds are preferred.

[0054] Examples of polyolefin compounds include those selected from paraffin wax and polyethylene wax, with a preferred weight-average molecular weight of 700 to 10,000, and more preferably 900 to 8,000.

[0055] Examples of fatty acid ester compounds include saturated or unsaturated monovalent or divalent aliphatic carboxylic acid esters, glycerol fatty acid esters, sorbitan fatty acid esters, and other fatty acid esters and their partially saponified products. Among these, mono or di fatty acid esters composed of a fatty acid having 11 to 28 carbon atoms, preferably 17 to 21 carbon atoms, and an alcohol are preferred.

[0056] Examples of fatty acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, adipic acid, and azelaic acid. Furthermore, fatty acids may also be alicyclic. Examples of alcohols include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have substituents such as aryl groups. Among these, monohydric or polyhydric saturated alcohols with 30 or fewer carbon atoms are preferred, and aliphatic saturated monohydric or polyhydric alcohols with 30 or fewer carbon atoms are more preferred. Here, "aliphatic" includes alicyclic compounds. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol. The above-mentioned ester compounds may contain aliphatic carboxylic acids and / or alcohols as impurities, and may also be mixtures of multiple compounds.

[0057] Specific examples of fatty acid ester compounds include glycerin monostearate, glycerin monobehenate, glycerin dibehenate, glycerin-12-hydroxymonostearate, sorbitan monobehenate, pentaerythritol monostearate, pentaerythritol distearate, stearyl stearate, and ethylene glycol montanate.

[0058] The release agent content is preferably 0.1 to 3 parts by mass, more preferably 0.2 to 2.5 parts by mass, and even more preferably 0.25 to 2 parts by mass, per 100 parts by mass of (A) aromatic polycarbonate resin. If it is less than 0.1 parts by mass, surface quality tends to deteriorate due to poor release during melt molding, while if it exceeds 3 parts by mass, the kneading workability of the resin composition tends to deteriorate, and clouding tends to occur on the surface of the molded article.

[0059] [Method for producing flame-retardant polycarbonate resin composition] There are no limitations on the method for producing the flame-retardant polycarbonate resin composition of the present invention, and a wide range of known methods for producing polycarbonate resin compositions can be employed. For example, an aromatic polycarbonate resin (A1), (A2) and (B) an organic sulfonic acid-based flame retardant that does not contain fluorine, and other components that may be added as needed are pre-mixed using various mixers such as a tumbler or Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, roll, braver, single-screw extruder, twin-screw extruder, or kneader. The melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320°C.

[0060] [Flame-retardant polycarbonate resin composition] The flame-retardant polycarbonate resin composition of the present invention contains less than 10 ppm of perfluorobutanesulfonic acid and its metal salts (PFBS) and less than 1000 ppm of polyfluoroalkyl compounds (PFAS), thus satisfying PFBS and PFAS regulations. PFAS regulations are being implemented by the EU / REACH and the US / EPA. According to the REACH definition, PFAS is a general term for perfluoroalkyl compounds, polyfluoroalkyl compounds, and their salts, i.e., compounds containing CF bonds. Therefore, in the present invention, PFAS also includes PFBS and targets compounds containing CF bonds. Currently, regulatory thresholds are being considered by each community, but based on past PFBS regulations as an example, it is assumed that a content of 1000 ppm or less will satisfy PFAS regulations.

[0061] [Molded products] The flame-retardant polycarbonate resin composition of the present invention can be used to produce various molded products by molding pellets obtained by pelletizing the above-mentioned flame-retardant polycarbonate resin composition using various molding methods. Alternatively, the resin, which is melt-kneaded in an extruder, can be directly molded into molded products without going through pellets.

[0062] To manufacture molded articles of the flame-retardant polycarbonate resin composition of the present invention, any molding method commonly used for polycarbonate resin compositions can be employed. Examples include injection molding, ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding methods such as gas-assisted molding, molding using insulated molds, molding using rapidly heated molds, foam molding (including supercritical fluids), insert molding, IMC (in-mold coating) molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, and blow molding. Molding methods using a hot runner system can also be used.

[0063] There are no restrictions on the shape, pattern, color, or dimensions of the molded product; these can be arbitrarily set according to the intended use of the product. Examples of molded products include electrical and electronic equipment, office automation equipment, information terminal equipment, machine parts, home appliances, vehicle (automobile) parts, building materials, various containers, amusement machines, leisure goods and miscellaneous items, lighting equipment parts, casings, etc. [Examples]

[0064] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples.

[0065] The raw materials used in the following examples and comparative examples are shown in Table 1 below. [Table 1]

[0066] (Examples) 3. Refer to Examples 1-2 and 4-8 (Comparative Examples 1-7) [Manufacturing of polycarbonate resin composition pellets] Each component listed in Table 1 above was blended in the proportions (parts by mass) shown in Table 3 below, mixed in a tumbler for 20 minutes, and then supplied from the upstream feeder to a Toshiba Machine Co., Ltd. twin-screw extruder (TEM26SX) equipped with one vent. The mixture was kneaded at a rotation speed of 250 rpm, a discharge rate of 30 kg / hour, and a barrel temperature of 280°C. The molten resin extruded into strands was rapidly cooled in a water bath and pelletized using a pelletizer to obtain pellets of the polycarbonate resin composition.

[0067] [Measurement of PFBS and PFAS content (unit: mass ppm)] The amount of PFBS in the composition was quantified by gas chromatography. Specifically, the polycarbonate resin composition obtained above was completely dissolved in methylene chloride, then methanol was added to precipitate the polycarbonate components, and methanol-soluble PFBS was quantified using a Shimadzu GC-2010. This method does not detect PTFE, so only PFBS can be accurately detected. In addition, the amount of PFAS in the resin composition was quantified by combustion ion chromatography. Specifically, the polycarbonate resin composition pellets obtained above were heated in an argon atmosphere at 270°C for 10 minutes using an AQF-100 automatic sample combustion device manufactured by Mitsubishi Chemical Analytec, and the amount of F ions generated was quantified using an ICS-90 manufactured by Nippon Dionex. In Table 3, "ND" indicates "not detected," meaning that the level was below the detection limit (1 ppm) and could not be detected.

[0068] [Flame retardancy assessment] After drying the pellets obtained by the manufacturing method described above at 120°C for 4 hours, they were injection molded using a Sumitomo Heavy Industries SE100DU injection molding machine under the conditions of a cylinder temperature of 280°C, a mold temperature of 80°C, and a molding cycle of 30 seconds to produce test specimens for UL combustion testing with a length of 125 mm, a width of 13 mm, and a thickness of 1.5 mm or 2.0 mm.

[0069] The flame retardancy was evaluated by conditioned the UL combustion test specimens obtained by the method described above in a constant temperature and humidity chamber at 23°C and 50% humidity for 48 hours, and then conducted in accordance with the UL94 test (combustion test for plastic materials for equipment components) as defined by UL in the United States.

[0070] The UL94-V test evaluates flame retardancy based on the afterflame time and drip properties after indirectly applying a burner flame to the lower end of a test specimen of a predetermined size, held vertically, for 10 seconds. To achieve flame retardancy of V-0, V-1, and V-2, the following criteria must be met:

[0071] [Table 2]

[0072] Here, afterflame time refers to the length of time the test specimen continues to burn with flame after the ignition source has been removed. Furthermore, cotton ignition by drip is determined by whether the marker cotton, located approximately 300 mm below the bottom of the test specimen, is ignited by the drippings from the test specimen. In addition, if even one of the five tests for a single material fails to meet the above criteria, it is evaluated as NR (not rated) and V-2 is not satisfied. The evaluation results are shown in Table 3 below.

[0073] [Table 3] [Industrial applicability]

[0074] The flame-retardant polycarbonate resin composition of the present invention complies with PFBS regulations and PFAS regulations, exhibits excellent flame retardancy, and has excellent moldability. Therefore, molded products can be suitably used in electrical and electronic equipment, office automation equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building materials, various containers, amusement machines, leisure goods and miscellaneous items, lighting equipment and other components.

Claims

1. (A) per 100 parts by mass of aromatic polycarbonate resin, (B) contains 0.05 to 0.3 parts by mass of a fluorine-free organic sulfonic acid flame retardant, (C) does not contain polytetrafluoroethylene, or if it does, the content is 0.09 parts by mass or less, and (B) the fluorine-free organic sulfonic acid flame retardant is polystyrene sulfonic acid or a metal salt thereof. A resin composition in which the amount of perfluorobutanesulfonic acid and its metal salt (PFBS) is less than 10 ppm and the amount of polyfluoroalkyl compound (PFAS) is less than 1000 ppm, (A) A flame-retardant polycarbonate resin composition characterized by comprising 50 to 100% by mass of aromatic polycarbonate resin (A1) having a dispersion degree (Mw / Mn) of 3.0 or higher as measured by GPC, and 50 to 0% by mass of aromatic polycarbonate resin (A2) having a dispersion degree (Mw / Mn) of less than 3.0 as measured by GPC.

2. A molded article of the flame-retardant polycarbonate resin composition according to claim 1.

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