Resin composition, pellet, and molded article

Abstract

To provide a resin composition having superior flame retardancy, impact resistance, and flowability, as well as a pellet and a molded article formed from the resin composition.SOLUTION: A resin composition comprising, relative to 100 pts.mass of a polycarbonate resin (A), 10 pts.mass or more to 35 pts.mass or less of a graft copolymer (B) comprising an aromatic vinyl monomer unit, a cyanovinyl monomer unit, and a diene rubber polymer unit, and 10 pts.mass or more to 40 pts.mass or less of a phosphate ester flame retardant (C), wherein the graft copolymer (B) has a melt mass flow rate (MFR) of 10 g / 10 min or less at 220°C under a load of 10 kg.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a pellet, and a molded article, and more particularly to a resin composition containing a polycarbonate resin as a main component. [Background technology]

[0002] Polycarbonate resin has excellent mechanical and thermal properties, and by imparting flame retardancy, it is used in a variety of applications, mainly in the fields of office automation equipment and electronic and electrical equipment. In recent years, with the trend toward thinner and lighter walls in office automation equipment, home appliances, and other applications, there has been an increasing demand for high-impact resin materials and highly flame-retardant resin materials. Specifically, Patent Document 1 discloses a polycarbonate resin composition containing 100 parts by weight of (A) polycarbonate resin (component A), 1 to 50 parts by weight of (B) a graft copolymer (component B) containing an aromatic vinyl monomer component, a vinyl cyanide monomer component, and a diene rubber polymer component, 1 to 10 parts by weight of (C) an impact modifier excluding component B (component C), and 10 to 30 parts by weight of (D) a phosphate ester flame retardant (component D), wherein the ratio (XImp / YImp) of the Charpy impact strength of the polycarbonate resin composition (XImp) to the Charpy impact strength of the polycarbonate resin composition not containing component D is 0.6 or more. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-12167 Summary of the Invention [Problem to be solved by the invention]

[0004] The resin composition described in Patent Document 1 is described as having excellent impact resistance and fluidity. However, when the present inventors investigated the resin composition described in the examples of Patent Document 1, they found that the flame retardancy, impact resistance, and fluidity were not necessarily sufficient. The present invention aims to solve the above problems and to provide a resin composition having excellent flame retardancy, impact resistance, and flowability, as well as pellets and molded articles formed from the resin composition. [Means for solving the problem]

[0005] As a result of investigations conducted by the present inventors in light of the above problems, the above problems were solved by the following means. <1> For 100 parts by mass of polycarbonate resin (A), 10 parts by mass or more and 35 parts by mass or less of a graft copolymer (B) containing an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a diene rubber polymer unit; and 10 parts by mass or more and 40 parts by mass or less of a phosphate ester flame retardant (C), The graft copolymer (B) has a melt mass flow rate (MFR) of 10 g / 10 min or less at 220° C. under a load of 10 kg. <2> the content of the impact improver other than the graft copolymer (B) is 0 parts by mass or more and less than 1 part by mass per 100 parts by mass of the polycarbonate resin (A); <1> The resin composition according to claim 1. <3> Further, the anti-dripping agent (D) is contained in an amount of 0.1 parts by mass or more and 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A), <1> or <2> The resin composition according to claim 1. <4> The phosphate ester-based flame retardant (C) is a phosphate ester represented by formula (P): <1> ~ <3> The resin composition according to any one of the above. Formula (P) [ka] (In formula (P), k is an integer of 0 to 5, and a mixture of compounds having different k numbers may be used. In the case of a mixture of phosphate esters having different k numbers, k is the average value of the mixture. X 1 represents a divalent arylene group, p, q, r, and s each independently represent 0 or 1, and R 11 , R 12 , R 13 and R 14 each independently represents an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms. <5> The content of the silicate mineral is 0 parts by mass or more and 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A). <1> ~ <4> The resin composition according to any one of the above. <6> Further, the anti-dripping agent (D) is contained in an amount of 0.1 parts by mass or more and 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A), the phosphate ester-based flame retardant (C) is a phosphate ester represented by formula (P), The content of the silicate mineral is 0 parts by mass or more and 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A). <1> ~ <5> The resin composition according to any one of the above. Formula (P) [ka] (In formula (P), k is an integer of 0 to 5, and a mixture of compounds having different k numbers may be used. In the case of a mixture of phosphate esters having different k numbers, k is the average value of the mixture. X 1 represents a divalent arylene group, p, q, r, and s each independently represent 0 or 1, and R 11 , R 12 , R 13 and R 14 each independently represents an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms. <7> the content of the impact improver other than the graft copolymer (B) is 0 parts by mass or more and less than 1 part by mass per 100 parts by mass of the polycarbonate resin (A); <6> The resin composition according to claim 1. <8> <1> ~ <7> A pellet of the resin composition according to any one of the above. <9> <1> ~ <7> A molded article formed from the resin composition according to any one of the above items. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a resin composition having excellent flame retardancy, impact resistance, and flowability, as well as pellets and molded articles formed from the resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0007] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the upper and lower limits. Furthermore, any combination of the upper and lower limit values ​​of the numerical values ​​in this specification is an example of this embodiment. In this specification, various physical properties and characteristic values ​​are those at 23°C unless otherwise specified. If the measurement methods, etc. described in the standards shown in this specification change from year to year, they will be based on the standards in effect as of January 1, 2024, unless otherwise specified. If the measurement methods, etc. described in the standards shown in this specification are abolished as of January 1, 2024, they will be based on the standards in effect at the time of abolition.

[0008] The resin composition of this embodiment contains 100 parts by mass of polycarbonate resin (A), 10 parts by mass or more and 35 parts by mass or less of graft copolymer (B) containing aromatic vinyl monomer units, vinyl cyanide monomer units, and diene rubber polymer units, and 10 parts by mass or more and 40 parts by mass or less of phosphate ester-based flame retardant (C), and is characterized in that the graft copolymer (B) has a melt mass flow rate (MFR) of 10 g / 10 min or less at 220°C and a 10 kg load. By adopting such a configuration, a resin composition excellent in flame retardancy, impact resistance, and fluidity can be obtained. In this embodiment, by incorporating a phosphate ester-based flame retardant (C), flame retardancy is achieved and a decrease in fluidity can be effectively suppressed. Furthermore, by incorporating a graft copolymer (B) as an impact modifier, impact resistance can be improved. In particular, by incorporating a graft copolymer (B) satisfying a predetermined MFR, the dispersibility of the diene rubber polymer units in the graft copolymer (B) can be improved. As a result, even with a small content of graft copolymer (B), excellent impact resistance can be achieved and flame retardancy and fluidity can also be improved. The present embodiment will be described in detail below.

[0009] <Polycarbonate resin (A)> The resin composition of the present embodiment contains a polycarbonate resin (A). The polycarbonate (A) resin is not particularly limited as long as it contains an -[OR-OC(=O)]- unit containing a carbonate bond in the molecular main chain (wherein R is an organic group, preferably a hydrocarbon group, more preferably an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear or branched structure). In this embodiment, the polycarbonate resin (A) is preferably an aromatic polycarbonate resin, and more preferably a polycarbonate resin having a bisphenol skeleton. By using such a polycarbonate resin, the obtained molded article can achieve better heat resistance and toughness. In this embodiment, the polycarbonate resin having a bisphenol skeleton preferably contains 90 mol % or more of all structural units of structural units having a bisphenol skeleton, more preferably 90 mol % or more of all structural units of structural units having at least one skeleton of bisphenol A, bisphenol C, and bisphenol AP, and even more preferably 90 mol % or more of all structural units of structural units having a bisphenol A skeleton.

[0010] The viscosity average molecular weight (Mv) of the polycarbonate resin (A) is preferably 10,000 or more, more preferably 12,000 or more, and even more preferably 15,000 or more. By setting it to be equal to or greater than the lower limit, the durability of the obtained molded article tends to be further improved. The upper limit of the viscosity average molecular weight (Mv) of the polycarbonate resin (A) is preferably 50,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less, still more preferably 25,000 or less, and even more preferably 20,000 or less. By setting it to be equal to or less than the upper limit, the molding processability of the molded article tends to be further improved. The viscosity average molecular weight (Mv) was 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 using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 ×Mv 0.83 , means the value calculated from When two or more types of polycarbonate resins (A) are used, the viscosity average molecular weight is the viscosity average molecular weight of the mixture.

[0011] The method for producing the polycarbonate resin (A) is not particularly limited, and polycarbonate resins produced by the conventionally known phosgene method (interfacial polymerization method) or melt method (ester interchange method) can be used. When the melt method is used, a polycarbonate resin with an adjusted amount of OH groups at the terminal groups can be used.

[0012] The polycarbonate resin (A) used in this embodiment may contain recycled products. Recycled products are polycarbonate resins derived from molded products formed from polycarbonate resin, meaning virgin polycarbonate resins that have been subjected to some kind of molding process, and include polycarbonate resin molded products, rejected polycarbonate resin molded products, scraps from the manufacture of polycarbonate resin molded products, etc. Molded products include injection molded products, extrusion molded products, and molded products formed by other manufacturing methods. Examples of recycled polycarbonate resin include those obtained by material recycling, in which recovered used polycarbonate resin molded products are crushed and alkaline washed to be reused as fibers, etc., those obtained by chemical recycling (chemical decomposition method), and those obtained by mechanical recycling. Chemical recycling involves chemically decomposing recovered used polycarbonate resin molded articles, returning them to their raw material level, and resynthesizing the polycarbonate resin.Mechanical recycling, on the other hand, is a method that makes it possible to remove dirt from polycarbonate resin molded articles more reliably than material recycling by carrying out alkaline washing more rigorously than in the material recycling described above, or by vacuum drying at high temperatures. For example, recycled polycarbonate resin can be obtained from used polycarbonate resin molded products by removing foreign matter, crushing and cleaning the product, and then pelletizing the product using an extruder. Examples of used polycarbonate resin molded products include discs, sheets (including films), meter covers, headlamp lenses, water bottles, and face plates for gaming and pachinko machines. The recycled product is preferably a polycarbonate resin in which 90 mol % or more of all constituent units are constituent units having a bisphenol A skeleton. Virgin products refer to products other than recycled products.

[0013] When the polycarbonate resin (A) contained in the resin composition of the present embodiment is blended, the proportion of recycled material is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, even more preferably 9 parts by mass or more, and may even be 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, or 35 parts by mass or more, per 100 parts by mass of the polycarbonate resin (A) (total of recycled and virgin materials). Furthermore, when blended, the proportion of the recycled product (preferably a recycled product of a polycarbonate resin containing a structural unit represented by formula (2)) is 100 parts by mass or less, preferably 90 parts by mass or less, preferably 75 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less, and may even be 35 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, 20 parts by mass or less, 15 parts by mass or less, or 12 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin. The resin composition of the present embodiment may contain only one type of recycled polycarbonate resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0014] In addition to the above, for details of the polycarbonate resin (A), please refer to the descriptions in paragraphs 0013 to 0041 of JP 2021-084942 A, the descriptions in paragraphs 0030 to 0035 of JP 2021-119211 A, and the descriptions in paragraphs 0008 to 0064 of JP 2023-012167 A, the contents of which are incorporated herein by reference.

[0015] The content of the polycarbonate resin (A) in the resin composition of this embodiment is preferably 45% by mass or more of the resin composition, more preferably 50% by mass or more, and even more preferably 55% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 65% ​​by mass or less. The resin composition of the present embodiment may contain only one type of polycarbonate resin (A), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0016] <Graft copolymer (B)> The resin composition of this embodiment contains a graft copolymer (B) containing aromatic vinyl monomer units, vinyl cyanide monomer units, and diene rubber polymer units. The graft copolymer (B) has a melt mass flow rate (MFR) of 10 g / 10 min or less at 220°C under a 10 kg load. By containing such a graft copolymer (B), the graft copolymer (B) has excellent dispersibility, and the impact resistance of the resulting molded article can be improved while effectively suppressing a decrease in flame retardancy and flowability. The melt mass flow rate (MFR) of the graft copolymer (B) at 220° C. under a load of 10 kg is preferably 8 g / 10 min or less, and more preferably 1 g / 10 min or more. When the resin composition of the present embodiment contains two or more types of graft copolymers (B), the MFR is the sum (weighted average value) of the values ​​obtained by multiplying the MFR of each graft copolymer (B) by the mass fraction of each graft copolymer (B).

[0017] The graft copolymer (B) is a graft copolymer containing aromatic vinyl monomer units, vinyl cyanide monomer units, and diene rubber polymer units. Examples of the graft copolymer (B) include ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer), and AAS resin (acrylonitrile-acrylic elastomer-styrene copolymer), among which ABS resin (acrylonitrile-butadiene-styrene copolymer) is preferred. The ABS resin may be a copolymer consisting of only acrylonitrile monomer, butadiene monomer, and styrene monomer, or may be copolymerized with other monomers in an amount of less than 10% by mass (preferably less than 5% by mass, more preferably less than 3% by mass, and particularly preferably less than 1% by mass). The same applies to other resins such as AES resin.

[0018] As the diene rubber polymer unit forming the ABS resin, for example, rubbers having a glass transition point of 10°C or less, such as polybutadiene, styrene-butadiene copolymer, and acrylonitrile-butadiene, are preferably used. Examples of the vinyl cyanide monomer grafted to the diene rubber polymer unit include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl monomer grafted to the diene rubber polymer unit include nucleus-substituted styrenes such as styrene, α-methylstyrene, and p-methylstyrene.

[0019] In the ABS resin used in this embodiment, the proportion of diene rubber polymer units in 100% by mass of the ABS resin component is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and is preferably 99% by mass or less, more preferably 65% ​​by mass or less, even more preferably 25% by mass or less. By making the proportion equal to or greater than the lower limit, impact resistance tends to be improved. Meanwhile, by making the proportion equal to or less than the upper limit, flame retardancy tends to be further improved.

[0020] In ABS resins, the weight-average particle size of the diene rubber polymer units is preferably 0.05 to 5.0 μm, more preferably 0.1 to 2.0 μm, and even more preferably 0.2 to 1.5 μm. The rubber particle size distribution may be either a single distribution or one with two or more peaks. Furthermore, the morphology may be either a single-phase distribution or a salami structure formed by the inclusion of an occluded phase around the rubber particles. The rubber particle size is determined by immersing the rubber polymer in a solution of OsO or RuO, staining it, observing it with a transmission electron microscope, and averaging the particle sizes measured for 1,000 or more particles. It has been well known that ABS resins contain copolymers of vinyl cyanide compounds and aromatic vinyl compounds that are not grafted onto diene rubber components. The ABS resin of this embodiment may contain free polymer components generated during the polymerization as described above, or may be a blend of a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound.

[0021] In the ABS resin of this embodiment, the ratio of vinyl cyanide monomer and aromatic vinyl monomer graft-polymerized to the diene rubber polymer units (the ratio of the mass of these monomer components to the mass of the diene rubber polymer units), i.e., the graft ratio, is preferably 1% by mass or more, more preferably 15% by mass or more, and preferably 99% by mass or less, more preferably 25% by mass or less. By setting the ratio at or above the lower limit, chemical resistance tends to be further improved. On the other hand, by setting the ratio at or below the upper limit, impact resistance tends to be further improved. Such an ABS resin may be produced by any method, such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, but is preferably produced by bulk polymerization. Furthermore, the better the dispersibility of the diene rubber polymer derived from ABS in the resin composition, the more impact resistance tends to be improved.

[0022] The content of the graft copolymer (B) in the resin composition of this embodiment is 10 parts by mass or more, preferably 12 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin (A), and is 35 parts by mass or less, preferably 34 parts by mass or less, and more preferably 32 parts by mass or less. By setting the content at or above the lower limit, impact resistance tends to be further improved. Meanwhile, by setting the content at or below the upper limit, flame retardancy tends to be further improved. The resin composition of the present embodiment may contain only one type of graft copolymer (B), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0023] The resin composition of the present embodiment may or may not contain an impact improver other than the graft copolymer (B).

[0024] When the resin composition of the present embodiment contains an impact improver other than the graft copolymer (B), the type of the impact improver is not particularly limited, but a core-shell elastomer is preferred. By using a core-shell elastomer in combination, impact resistance tends to be further improved. When the resin composition of this embodiment contains an impact improver other than the graft copolymer (B) (preferably a core-shell elastomer), the content thereof is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.8 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin. By setting the content at or above the lower limit, impact resistance tends to be further improved. Meanwhile, by setting the content at or below the upper limit, flame retardancy tends to be further improved. Furthermore, when the resin composition of this embodiment contains an impact improver (preferably a core-shell elastomer) other than the graft copolymer (B), the content thereof is preferably 0.01 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 3 parts by mass or less, more preferably 1.5 parts by mass or less, per 100 parts by mass of the graft copolymer (B). By setting the content to be equal to or greater than the lower limit, impact resistance tends to be further improved. Meanwhile, by setting the content to be equal to or less than the upper limit, flame retardancy tends to be further improved. The resin composition of the present embodiment may contain only one type of impact modifier other than the graft copolymer (B), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0025] The core-shell elastomer is particularly preferably a core-shell elastomer having a core layer made of at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, and an IPN-type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and a shell layer formed by copolymerizing a (meth)acrylic acid ester around the core layer. The core-shell elastomer preferably contains 40% by mass or more of the rubber component, more preferably 60% by mass or more. Furthermore, the (meth)acrylic acid content is preferably 10% by mass or more. Note that the core-shell elastomer in this embodiment does not necessarily have a clearly distinguishable core layer and shell layer; it is intended to broadly include compounds obtained by graft-polymerizing a rubber component around the core portion.

[0026] Preferred specific examples of core-shell elastomers 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, and the like.

[0027] Examples of such core-shell elastomers include "PARALOID (registered trademark, the same applies hereinafter) EXL2602," "PARALOID EXL2603," "PARALOID EXL2655," "PARALOID EXL2311," "PARALOID EXL2313," "PARALOID EXL2315," "PARALOID KM330," "PARALOID KM336P," and "PARALOID KCZ201," all manufactured by Rohm and Haas Japan; "METABLEN (registered trademark, the same applies hereinafter) C-223A," "METABLEN E-901," "METABLEN S-2001," and "METABLEN SRK-200," all manufactured by Mitsubishi Chemical Corporation; "KANE ACE (registered trademark, the same applies hereinafter) M-511," "KANE ACE M-600," "KANE ACE M-400," "KANE ACE M-580," "KANE ACE M-711," and "KANE ACE MR-01," all manufactured by Kaneka Corporation; and "UBESTA XPA," all manufactured by UBE Corporation.

[0028] The resin composition of this embodiment may also be configured to be substantially free of impact modifiers other than the graft copolymer (B). When substantially free of impact modifiers, the content of the impact modifiers other than the graft copolymer (B) in the resin composition of this embodiment is preferably 0 parts by mass or more and less than 1 part by mass, more preferably 0 parts by mass or more and less than 0.1 parts by mass, and even more preferably 0 parts by mass or more and less than 0.01 parts by mass, per 100 parts by mass of the polycarbonate resin (A). By configuring the resin composition to be substantially free of impact modifiers other than the graft copolymer (B), the flame retardancy and flowability of the resin composition tend to be further improved.

[0029] <Phosphate ester flame retardant (C)> The resin composition of this embodiment contains a phosphate ester-based flame retardant (C). By containing the phosphate ester-based flame retardant (C), the flame retardancy of the resulting molded article can be improved. Furthermore, the flowability of the resin composition also tends to be improved. The phosphate ester flame retardant (C) is preferably a condensed phosphate ester flame retardant, more preferably a condensed phosphate ester flame retardant represented by formula (P). Formula (P) [ka] (In formula (P), k is an integer of 0 to 5, and a mixture of compounds having different k numbers may be used. In the case of a mixture of phosphate esters having different k numbers, k is the average value of the mixture. X 1 represents a divalent arylene group, p, q, r, and s each independently represent 0 or 1, and R 11 , R 12 , R 13 and R 14 each independently represents an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms.

[0030] In formula (P), the compound may be a mixture of compounds having different k values, and in the case of a mixture of condensed phosphate esters having different k values, k is the average value of the mixture. k is usually an integer of 0 to 5, and in the case of a mixture of compounds having different k values, the average k value is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.8 or more, particularly preferably 0.95 or more, and is preferably 2 or less, more preferably 1.5 or less, even more preferably 1.2 or less, particularly preferably 1.15 or less.

[0031] Also, X 1 represents a divalent arylene group, for example, a divalent group derived from a dihydroxy compound such as resorcinol, hydroquinone, bisphenol A, 2,2'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, or 2,7-dihydroxynaphthalene. Of these, divalent groups derived from resorcinol, bisphenol A, or 3,3'-dihydroxybiphenyl are particularly preferred.

[0032] In formula (P), p, q, r and s each independently represent 0 or 1, with 1 being preferred.

[0033] R in formula (P) 11 , R 12 , R 13 and R 14and respectively represent an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms. Examples of such an aryl group include a phenyl group, a cresyl group, a xylyl group, an isopropylphenyl group, a butylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, and a p-cumylphenyl group, with a phenyl group, a cresyl group, and a xylyl group being more preferred.

[0034] Specific examples of the condensed phosphate ester-based flame retardant represented by formula (P) include aromatic phosphate esters such as triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis-(tert-butylphenyl)phenyl phosphate, tris-(tert-butylphenyl)phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, and tris-(isopropylphenyl)phosphate; and condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), and biphenyl bis-diphenyl phosphate.

[0035] The acid value of the condensed phosphate ester flame retardant represented by formula (P) is preferably 0.2 mg KOH / g or less, more preferably 0.15 mg KOH / g or less, even more preferably 0.1 mg KOH or less, and particularly preferably 0.05 mg KOH / g or less. The lower limit of the acid value can be set to substantially 0. The content of half ester in the condensed phosphate ester flame retardant represented by formula (P) is preferably 1 mass% or less, more preferably 0.5 mass% or less. By setting the acid value to 0.2 mg KOH / g or less and the half ester content to 1 mass% or less, the thermal stability and hydrolysis resistance of the resulting molded article tend to be further improved.

[0036] The phosphate ester-based flame retardant (C) includes, in addition to the above, polyester resins, polycarbonate resins, and epoxy resins containing a phosphate ester moiety. Please also refer to paragraphs 0030 to 0034 of International Publication No. 2017 / 038737, the contents of which are incorporated herein by reference.

[0037] The content of the phosphate ester-based flame retardant (C) in the resin composition of this embodiment is 10 parts by mass or more, preferably 12 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 18 parts by mass or more, per 100 parts by mass of the (A) polycarbonate resin. By ensuring that the content is above the lower limit, char formation during combustion of the resulting molded article can be promoted, further improving flame retardancy. Furthermore, the content of the phosphate ester-based flame retardant (C) is 40 parts by mass or less, preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less, per 100 parts by mass of the (A) polycarbonate resin. By ensuring that the content is below the upper limit, impact resistance and drip prevention during combustion are improved, and pellet manufacturability also tends to be improved. The resin composition of the present embodiment may contain only one type of phosphate ester-based flame retardant (C), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0038] The resin composition of the present embodiment may or may not contain a flame retardant other than the phosphate ester-based flame retardant (C). Examples of the flame retardant other than the phosphate ester-based flame retardant (C) include alkali metal salts and halogen-based flame retardants. An example of the resin composition of this embodiment is one that is substantially free of flame retardants other than the phosphate ester-based flame retardant (C). "Substantially free" means that the content of flame retardants other than the phosphate ester-based flame retardant (C) among the flame retardants contained in the resin composition is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less of the content of flame retardants other than the phosphate ester-based flame retardant (C).

[0039] <Anti-sagging agent (D)> The resin composition of the present embodiment preferably contains an anti-dripping agent (D). The anti-dripping agent (D) preferably contains a fluoropolymer having fibril-forming ability. Fibril-forming fluoropolymers are easily dispersed in resin compositions and tend to bond together to form fibrous structures. The fluoropolymer capable of forming fibrils preferably has an extremely high molecular weight of 1,000,000 to 10,000,000, and exhibits a tendency to bond together to form fibers under external action such as shear force. Preferred fluoropolymers include tetrafluoroethylene (PTFE) resin, perfluoroalkoxy (PFA) resin, and fluorinated ethylene propylene (FEP) resin, with polytetrafluoroethylene being particularly preferred.

[0040] Examples of fluoropolymers capable of forming fibrils include Teflon (registered trademark) 6J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd. and Polyflon manufactured by Daikin Industries, Ltd.

[0041] It is also preferable to use the fluoropolymer in the form of an aqueous dispersion. This dispersion is an aqueous dispersion produced by adding a surfactant to a fluororesin latex obtained by ordinary emulsion polymerization, followed by concentration and stabilization. The content of the fluoropolymer in the aqueous dispersion is preferably 20 to 80% by mass, particularly 30 to 70% by mass. Examples of aqueous dispersions of polytetrafluoroethylene include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemicals Co., Ltd., Fluon D-1 manufactured by Daikin Industries, Ltd., and polytetrafluoroethylene polymers having a multilayer structure obtained by polymerizing vinyl monomers, such as Metablen A-3800 manufactured by Mitsubishi Rayon Co., Ltd.

[0042] The fibril-forming fluoropolymer preferably has a primary particle size in the range of 0.05 to 1.0 μm, more preferably 0.1 to 0.5 μm. In the resin composition, the fluoropolymer is preferably in the form of fibrils having a thickness of 0.5 microns or less, and the fibrils preferably exist in a network structure and / or branched form.

[0043] The content of the anti-dripping agent (D) in the resin composition of this embodiment is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, per 100 parts by mass of the (A) polycarbonate resin. By making the content equal to or greater than the lower limit, the anti-dripping effect tends to be effectively exerted. Furthermore, the content of the anti-dripping agent (D) is preferably 1 part by mass or less, more preferably 0.8 parts by mass or less, and even more preferably 0.5 parts by mass or less, per 100 parts by mass of the (A) polycarbonate resin. By making the content equal to or less than the upper limit, the mechanical strength of the obtained molded article tends to be improved, and the appearance also tends to be improved. The resin composition of the present embodiment may contain only one type of anti-dripping agent (D), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0044] <Stabilizer> The resin composition of the present embodiment may contain a stabilizer. The stabilizer includes a heat stabilizer and an antioxidant. Examples of the stabilizer include phenol-based, amine-based, phosphorus-based, and thioether-based stabilizers. Among these, in this embodiment, it is preferable to use a phosphorus-based heat stabilizer.

[0045] Any known phosphorus-based heat 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.

[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, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, distearyl pentaerythritol diphosphite, bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, and bis(nonylphenyl)pentaerythritol diphosphite. Specific examples of such organic phosphite compounds include "ADK STAB (registered trademark; the same applies hereinafter) 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 (registered trademark; the same applies hereinafter) 168" manufactured by BASF.

[0047] In addition to the above, the phosphorus-based heat stabilizer used in this embodiment can be found in paragraphs 0127 to 0133 of Japanese Patent Application Laid-Open No. 2022-067329, the contents of which are incorporated herein by reference.

[0048] As the phenol-based antioxidant, a hindered phenol-based antioxidant is preferably used. Specific examples of hindered phenol antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylene bis[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, 4,6-bis(octyl methylthiomethyl)-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 hindered phenol antioxidants include "Irganox (registered trademark; the same applies hereinafter) 1010" and "Irganox 1076" manufactured by BASF, and "ADK STAB AO-50" and "ADK STAB AO-60" manufactured by ADEKA.

[0050] The content of the stabilizer in the resin composition of this embodiment is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, more preferably 0.01 part by mass or more, even more preferably 0.1 part by mass or more, and still more preferably 0.5 part by mass or more, relative to 100 parts by mass of the polycarbonate resin (A), and is preferably 3 parts by mass or less, more preferably 2 parts by mass or less. By setting the content of the stabilizer within the above range, the effect of adding the stabilizer can be more effectively exerted. The resin composition of the present embodiment may contain only one stabilizer, or may contain two or more stabilizers. When two or more stabilizers are contained, the total amount is preferably in the above range.

[0051] <Release agent> The resin composition of the present embodiment may contain a release agent. Examples of the release agent include aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane-based silicone oils, ketone waxes, and light amides, and the like are preferred.

[0052] 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, tetratriacontanoic acid, montanic acid, adipic acid, and azelaic acid. Examples of salts of aliphatic carboxylic acids include sodium salts, potassium salts, calcium salts, and magnesium salts.

[0053] 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 or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferred.

[0054] 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.

[0055] 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.

[0056] 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. Note that the aliphatic hydrocarbons herein also include alicyclic hydrocarbons. The number average molecular weight of the aliphatic hydrocarbons is preferably 5,000 or less. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferred, and paraffin wax and polyethylene wax are more preferred.

[0057] For details about the release agent, please refer to paragraphs 0055 to 0061 of JP 2018-095706 A, the contents of which are incorporated herein by reference.

[0058] When the resin composition of the present embodiment contains a release agent, the content thereof in the resin composition is preferably 0.05 to 3 mass %, more preferably 0.1 to 0.8 mass %, and even more preferably 0.1 to 0.6 mass %. The resin composition of the present embodiment may contain only one type of release agent, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0059] <Coloring agent> The resin composition of the present embodiment may contain a colorant. By containing a colorant, it is possible to impart color to the resulting molded article. The colorant may be a pigment or a dye, but is preferably a pigment. The colorant may be either an achromatic colorant or a chromatic colorant, with an achromatic colorant being preferred. Also preferred is a black colorant composed of two or more chromatic colorants. In this embodiment, preferred examples of the colorant include a black colorant (preferably a black pigment) and / or a white colorant (preferably a white pigment). An example of a black pigment is carbon black. For carbon black, the descriptions in paragraphs 0065 to 0068 of JP 2021-031633 A and paragraphs 0014 to 0025 of JP 2019-056035 A can be referred to, the contents of which are incorporated herein by reference. An example of the white pigment is titanium oxide. Pigments such as carbon black may be blended as a masterbatch with a thermoplastic resin (preferably a polycarbonate resin and / or a styrene resin, more preferably a styrene resin). The carbon black content in the masterbatch is preferably 10 to 60% by mass.

[0060] The content of the colorant in the resin composition of this embodiment is preferably 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, even more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, even more preferably 0.05 parts by mass or more, and even more preferably 0.10 parts by mass or more, per 100 parts by mass of the polycarbonate resin (A). By ensuring that the content is above the lower limit, color development can be fully achieved. Furthermore, the content of the colorant in the resin composition of this embodiment is preferably 10.00 parts by mass or less, more preferably 5.00 parts by mass or less, even more preferably 3.00 parts by mass or less, even more preferably 1.00 parts by mass or less, and even more preferably 0.50 parts by mass or less, per 100 parts by mass of the polycarbonate resin and the other thermoplastic resin combined. By ensuring that the content is below the upper limit, problems such as mold contamination during injection molding can be effectively suppressed. The resin composition of the present embodiment may contain only one type of colorant, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0061] <Other ingredients> The resin composition of the present embodiment may contain other components as needed, as long as the desired physical properties are not significantly impaired. Examples of the other components include fillers, resin components other than those described above, such as the polycarbonate resin (A), and various resin additives. Examples of resin additives include reactive compounds, ultraviolet absorbers, antistatic agents, flame retardants, flame retardant assistants, antifogging agents, antiblocking agents, flow improvers, plasticizers, dispersants, antibacterial agents, etc. One type of resin additive may be contained, or two or more types may be contained in any combination and ratio. In the resin composition of this embodiment, the polycarbonate resin (A), the graft copolymer (B), and the phosphate ester-based flame retardant (C) preferably account for 90% by mass or more of the resin composition, more preferably 95% by mass or more, and even more preferably 98% by mass or more. Furthermore, the total of the polycarbonate resin (A), the graft copolymer (B), the phosphate ester flame retardant (C), and (D) the anti-drip agent, stabilizer, release agent, and colorant, which are blended as needed, preferably accounts for 95% by mass or more of the resin composition, more preferably 97% by mass or more, and even more preferably 99% by mass or more. In the resin composition of this embodiment, the content of the silicate mineral is preferably 0 to 1 part by mass, more preferably 0 to less than 0.5 parts by mass, even more preferably 0 to less than 0.1 parts by mass, still more preferably 0 to less than 0.05 parts by mass, and even more preferably 0 to less than 0.01 parts by mass, relative to 100 parts by mass of the polycarbonate resin (A). By adopting such a configuration, the impact resistance of the resulting molded article tends to be further improved. An example of a silicate mineral is talc.

[0062] <Physical properties of resin composition> The resin composition of the present embodiment preferably has excellent fluidity. Specifically, the melt mass flow rate (MFR) of the resin composition at 220°C under a 10 kg load is preferably 20 g / 10 min or more, more preferably 25 g / 10 min or more, even more preferably 30 g / 10 min or more, even more preferably 35 g / 10 min or more, and even more preferably 40 g / 10 min or more, and is preferably 70 g / 10 min or less, more preferably 60 g / 10 min or less, and may be 55 g / 10 min or less.

[0063] The resin composition of the present embodiment preferably has excellent impact resistance. Specifically, an ISO multipurpose test piece (3.0 mm thick) formed from the resin composition was used, and the notched Charpy impact strength (unit: kJ / m) was measured at a temperature of 23°C based on ISO standard 179-1. 2 ) is 10kJ / m 2 It is preferable that the concentration is 15 kJ / m or more. 2 More preferably, it is 25 kJ / m or more. 2 More preferably, it is 30 kJ / m or more. 2 More preferably, it is 35 kJ / m or more. 2 The upper limit is not particularly specified, but for example, 55 kJ / m 2 The following is practical:

[0064] In addition, the resin composition of the present embodiment preferably has excellent flame retardancy. Specifically, it is preferable that the flame retardancy satisfies V-0 when measured in accordance with the UL-94 standard using a 1.5 mm thick test piece formed from the resin composition. The MFR, Charpy impact strength, and flame retardancy are measured according to the methods described in the examples below.

[0065] <Method of manufacturing resin composition> The method for producing the resin composition of this embodiment is not limited, and a wide variety of known methods for producing resin compositions can be used. For example, the polycarbonate resin (A), the graft copolymer (B), the phosphate ester-based flame retardant (C), and other components that are added as needed may be premixed using a mixer such as a tumbler or a Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, a roll, a Brabender mixer, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader. The melt-kneading temperature is not particularly limited, but is usually in the range of 240 to 320°C.

[0066] <Molded products> The molded article of this embodiment is formed from the resin composition or pellets of this embodiment. The resin composition of this embodiment can also be molded directly without first going through the pellet state. The resin composition (e.g., pellets) described above can be molded into a molded article by various molding methods. The shape of the molded article is not particularly limited and can be appropriately selected depending on the application and purpose of the molded article. Examples of the shape include film, rod, cylinder, ring, circle, ellipse, polygon, irregular shape, hollow, frame, box, panel, button, etc.

[0067] The method for forming the molded article is not particularly limited, and conventionally known molding methods can be used, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, gas-assisted blow molding, blow molding, extrusion blow molding, IMC (in-mold coating) molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding. The resin composition of this embodiment is particularly suitable for molded articles obtained by injection molding, injection compression molding, and extrusion molding. However, it goes without saying that the resin composition of this embodiment is not limited to molded articles obtained by these methods.

[0068] The molded article of this embodiment can be widely used for molded articles containing polycarbonate resin. Specifically, it is preferably used in electrical and electronic equipment / components, office automation equipment / components, information terminal equipment / components, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods and sundries, lighting equipment, etc. It is particularly preferably used for thin-walled molded products (for example, thin-walled molded products with a thickness of 1 μm or more and 1 mm or less at the thinnest part). [Example]

[0069] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0070] 1. Raw materials The raw materials shown in Table 1 below were used. [Table 1]

[0071] 2. Examples 1 to 6 and Comparative Examples 1 to 5 <Preparation of resin pellets> The components listed in Table 1 were blended in the proportions shown in Table 3 or Table 4 (each component is in parts by mass), and the mixture was mixed uniformly in a tumbler mixer to prepare a mixture. This mixture was fed into a twin-screw extruder ("TEX30α" manufactured by The Japan Steel Works, Ltd.), kneaded under conditions of a screw rotation of 200 rpm, a discharge rate of 30 kg / hour, and a barrel temperature of 280°C, and extruded in the form of strands from the tip of the nozzle. The extrudate was quenched in a water bath and cut into pellets using a pelletizer to obtain pellets of the resin composition.

[0072] <Melt Mass Flow Rate (MFR)> The MFR of the graft copolymer and the resin composition was measured at 220°C under a load of 10 kg in accordance with ISO1133. The unit is g / 10 min.

[0073] <Impact resistance> The obtained pellets were dried at 80°C for 5 hours and then injection-molded in an injection molding machine (NEX80III manufactured by Nissei Plastic Industrial Co., Ltd.) at a cylinder temperature of 260°C, a mold temperature of 60°C, a screw rotation speed of 80 rpm, and an injection speed of 30 mm / s to produce ISO multipurpose test specimens (3.0 mmt). Using the obtained ISO multipurpose test piece (3.0 mm thick), the notched Charpy impact strength (unit: kJ / m) was measured at a temperature of 23°C in accordance with ISO standard 179-1. 2 ) was measured.

[0074] <Flammability> The pellets of the resin composition obtained above were injection molded using an injection molding machine ("SE50DUZ" manufactured by Sumitomo Heavy Industries, Ltd.) under conditions of a resin temperature of 290°C and a mold temperature of 80°C, to obtain UL test specimens having a length of 127 mm, a width of 12.7 mm and a thickness of 1.5 mm. The obtained UL test specimens were conditioned for 48 hours in a temperature-controlled room at 23°C and a relative humidity of 50%, and then tested in accordance with the UL94 test (combustion test for plastic materials for equipment parts) established by Underwriters Laboratories (UL) of the United States. The UL94 test is a method of evaluating flame retardancy based on the afterflame time and drip rate after a burner flame is applied to a test piece held vertically for 10 seconds. To achieve flame retardancy of V-0, V-1, or V-2, the material must meet the standards shown in Table 2 below.

[0075] [Table 2]

[0076] [Table 3]

[0077] [Table 4]

[0078] The unit of the above MFR is g / 10 min, and the unit of impact resistance is kJ / m 2 Regarding flame retardancy, if V-2 is not met, it is indicated as NR (not rated). As is clear from the above results, the resin compositions of the present invention were excellent in flame retardancy, impact resistance, and flowability (Examples 1 to 6). In contrast, when the MFR of the graft copolymer (B) was high (Comparative Examples 1 to 3), the impact resistance or flame retardancy was poor. Furthermore, when the content of graft copolymer (B) was high (Comparative Example 4), the flame retardancy was poor, whereas when the content of graft copolymer (B) was low (Comparative Example 5), the flowability and impact resistance were poor.

Claims

1. For 100 parts by mass of the polycarbonate resin (A), 10 parts by mass or more and 35 parts by mass or less of a graft copolymer (B) containing an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a diene rubber polymer unit; and 10 parts by mass or more and 40 parts by mass or less of a phosphate ester-based flame retardant (C), The graft copolymer (B) has a melt mass flow rate (MFR) of 10 g / 10 min or less at 220° C. under a load of 10 kg.

2. 2. The resin composition according to claim 1, wherein the content of the impact modifier other than the graft copolymer (B) is 0 parts by mass or more and less than 1 part by mass per 100 parts by mass of the polycarbonate resin (A).

3. The resin composition according to claim 1 or 2, further comprising an anti-dripping agent (D) in an amount of 0.1 part by mass or more and 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A).

4. The resin composition according to claim 1 or 2, wherein the phosphate ester-based flame retardant (C) is a phosphate ester represented by formula (P): Formula (P) 【Chemical 1】 (In formula (P), k is an integer of 0 to 5, and a mixture of compounds having different k values ​​may be used. In the case of a mixture of phosphate esters having different k values, k is the average value of the mixture. X １ represents a divalent arylene group, p, q, r, and s each independently represent 0 or 1, and R 11 , R 12 , R 13 and R 14 each independently represents an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms.

5. The resin composition according to claim 1 or 2, wherein the content of the silicate mineral is 0 part by mass or more and 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A).

6. the content of the impact improver other than the graft copolymer (B) is 0 parts by mass or more and less than 1 part by mass per 100 parts by mass of the polycarbonate resin (A), Further, the composition contains an anti-dripping agent (D) in an amount of 0.1 parts by mass or more and 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A), The phosphate ester-based flame retardant (C) is a phosphate ester represented by formula (P), The resin composition according to claim 1, wherein the content of the silicate mineral is 0 part by mass or more and 1 part by mass or less per 100 parts by mass of the polycarbonate resin (A). Formula (P) 【Chemistry 2】 (In formula (P), k is an integer of 0 to 5, and a mixture of compounds having different k values ​​may be used. In the case of a mixture of phosphate esters having different k values, k is the average value of the mixture. X １ represents a divalent arylene group, p, q, r, and s each independently represent 0 or 1, and R 11 , R 12 , R 13 and R 14 each independently represents an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group having 1 to 6 carbon atoms.

7. 7. The resin composition according to claim 6, wherein the content of the impact improver other than the graft copolymer (B) is 0 part by mass or more and less than 1 part by mass per 100 parts by mass of the polycarbonate resin (A).

8. Pellets of the resin composition according to claim 1, 2 or 6.

9. A molded article formed from the resin composition according to claim 1, 2 or 6.

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