Polycarbonate resin composition and shaped article

Abstract

Provided is a resin composition containing a polycarbonate resin (A), an amorphous polyester resin (B), a core-shell elastic body (C), and a flame retardant (D). The (B) content is 15-35 wt% of the total of the (A) and the (B). The (B) comprises a glycol-modified polyethylene terephthalate (b1). The (b1) content is 15-100 wt% of the (B). The (C) content is 1-30 parts by weight per 100 parts by weight total of the (A) and the (B). The volume-average particle size of the (C) is at least 100 nm. The (C) comprises a phosphoric acid emulsifier or a sulfonic acid emulsifier as an emulsifier.

Description

Polycarbonate resin composition and molded article

[0001] The present invention relates to a resin composition containing a polycarbonate resin and a molded article thereof.

[0002] Molded articles made from polycarbonate resins have excellent transparency, impact resistance, heat resistance, dimensional stability, and self-extinguishing properties (flame retardancy), and are used in a wide range of fields, including electrical, electronic, and office equipment, optical components, precision machinery, automobiles, security and medical care, building materials, and miscellaneous goods.

[0003] Known methods for improving the impact resistance of molded articles made of polycarbonate resins include blending a crystalline polyester resin or a thermoplastic elastomer component with the polycarbonate resin (see, for example, Patent Documents 1 to 3). It is also known to impart flame retardancy to the polycarbonate resin by blending a flame retardant with the polycarbonate resin (see, for example, Patent Document 3).

[0004] US Patent No. 5,369,154 JP 2012-184445 A JP 2015-117376 A

[0005] In conventional polycarbonate resin compositions, improving impact resistance tends to result in a decrease in flame retardancy, making it difficult to achieve both high impact resistance and good flame retardancy. Furthermore, polycarbonate resins generally have low fluidity when melted, so there is a need to improve the fluidity when melted to improve melt processability.

[0006] In view of the above-mentioned current situation, an object of the present invention is to provide a polycarbonate resin composition having a good balance of impact resistance, flame retardancy, and fluidity when melted, and a molded article thereof.

[0007] As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by blending a specific type of amorphous polyester resin, a core-shell elastomer having a specific particle size and containing a specific emulsifier, and a flame retardant in a specific composition with a polycarbonate resin, and have arrived at the present invention. That is, the present invention provides a flame retardant comprising a polycarbonate resin (A), an amorphous polyester resin (B), a core-shell elastomer (C), and a flame retardant (D), wherein the content of the amorphous polyester resin (B) is 15 to 35% by weight of the total of the polycarbonate resin (A) and the amorphous polyester resin (B), the amorphous polyester resin (B) contains a glycol-modified polyethylene terephthalate (b1), and the content of the glycol-modified polyethylene terephthalate (b1) in the amorphous polyester resin (B) is 15 to 100% by weight, the content of the core-shell elastomer (C) is 1 to 30 parts by weight per 100 parts by weight of the total of the polycarbonate resin (A) and the amorphous polyester resin (B), and the volume average particle diameter of the core-shell elastomer (C) is 100 nm or more, The core-shell type elastomer (C) relates to a resin composition containing a phosphoric acid-based emulsifier or a sulfonic acid-based emulsifier as an emulsifier.

[0008] According to the present invention, it is possible to provide a polycarbonate resin composition having a good balance of impact resistance, flame retardancy, and fluidity in a melt, and a molded article thereof. Furthermore, according to a preferred embodiment of the present invention, it is possible to improve the flame retardancy, which has the advantage of allowing the amount of flame retardant to be reduced in the polycarbonate resin composition.

[0009] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The polycarbonate resin composition according to the present disclosure contains at least a polycarbonate resin (A), an amorphous polyester resin (B), a core-shell elastomer (C), and a flame retardant (D).

[0010] <Polycarbonate-based resin (A)> As the polycarbonate-based resin (A), a commonly used polycarbonate-based resin can be used, for example, a polycarbonate-based resin produced by a method of interfacial polycondensation of a dihydric phenol and a carbonyl halide, or a method of melt polymerization of a dihydric phenol and a carbonate diester (transesterification method), or the like.

[0011] Examples of the dihydric phenol include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, hydroquinone, resorcinol, and catechol. Among these, bis(hydroxyphenyl)alkanes are preferred, and 2,2-bis(4-hydroxyphenyl)propane is particularly preferred.

[0012] Examples of carbonate precursors include carbonyl halides, carbonyl esters, and haloformates. Specific examples include phosgene, diaryl carbonates such as dihaloformates of dihydric phenols, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, and m-cresyl carbonate, and aliphatic carbonate compounds such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dibutyl carbonate, diamyl carbonate, and dioctyl carbonate.

[0013] The polycarbonate resin may be a resin in which the molecular structure of the polymer chain is a straight-chain structure, or a resin having a branched structure. Examples of branching agents for introducing such a branched structure include 1,1,1-tris(4-hydroxyphenyl)ethane, α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, phloroglucin, trimellitic acid, and isatin bis(o-cresol). Furthermore, examples of molecular weight modifiers that can be used include phenol, p-t-butylphenol, p-t-octylphenol, and p-cumylphenol.

[0014] The polycarbonate resin may be a polymer having only polycarbonate structural units produced using only the dihydric phenol and a carbonate precursor, a copolymer having polycarbonate structural units and polyorganosiloxane structural units, or a resin composition containing the polymer and the copolymer. It may also be a polyester-polycarbonate resin obtained by polymerizing a dihydric phenol or the like in the presence of a difunctional carboxylic acid such as terephthalic acid or an ester-forming precursor thereof.

[0015] <Amorphous polyester resin (B)> The polycarbonate resin composition according to the present disclosure contains an amorphous polyester resin (B). By blending the amorphous polyester resin (B), crystallization of the polyester phase in the polycarbonate resin composition is suppressed, distortion caused by the polyester phase is less likely to occur, and the impact strength and flame retardancy of the polycarbonate resin composition can be improved.

[0016] The polyester resin may be an aromatic polyester having a structure in which an aromatic dicarboxylic acid or its ester derivative component and a diol component such as an aliphatic diol or an alicyclic diol are linked by an ester reaction. For example, the polyester resin may be one obtained by polycondensing the above-mentioned components by a known method.

[0017] The aromatic dicarboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4'-p-terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, etc. One type of aromatic dicarboxylic acid may be used alone, or two or more types may be used in combination.

[0018] The aliphatic diol is not particularly limited, but examples thereof include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, etc. The alicyclic diol includes, for example, 1,4-cyclohexanedimethanol, etc. As the diol component, only one type may be used, or two or more types may be used in combination.

[0019] The polyester resin may have a structural component derived from a tri- or higher functional monomer such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, or pyromellitic acid.

[0020] The amorphous polyester resin of component (B) can usually be confirmed by the absence of a clear endothermic peak in differential scanning calorimetry (DSC). Specifically, a clear endothermic peak refers to a peak whose half-width is, for example, within 15° when measured in differential scanning calorimetry (DSC) at a heating rate of 10°C / min. Conversely, a polyester resin having a clear endothermic peak is called a crystalline polyester resin.

[0021] The amorphous polyester resin usually has a relatively high glass transition temperature (Tg). Specifically, the amorphous polyester resin preferably has a Tg of 40 to 90° C., more preferably 45 to 85° C. The Tg can be measured using a differential scanning calorimeter.

[0022] In the polycarbonate resin composition according to the present disclosure, the content of the amorphous polyester resin (B) is 15 to 35 wt% of the total of the polycarbonate resin (A) and the amorphous polyester resin (B). If the content of the amorphous polyester resin (B) is less than 15 wt%, good impact resistance may not be achieved, or the fluidity during melting may be insufficient. If the content exceeds 35 wt%, good impact resistance and / or flame retardancy may not be achieved. The content of the amorphous polyester resin (B) is preferably 20 to 35 wt%, and more preferably 25 to 30 wt%.

[0023] In the polycarbonate resin composition according to the present disclosure, the amorphous polyester resin (B) contains at least a glycol-modified polyethylene terephthalate (b1), which can improve the impact resistance and / or flame retardancy of the polycarbonate resin composition.

[0024] The glycol-modified polyethylene terephthalate (b1) refers to a copolymer containing at least terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol (CHDM) as monomer components. Specific examples include PETG resin and PCT resin. Only one of these may be used, or two or more may be used in combination. Of these, it is preferable to use PETG resin.

[0025] Commercially available PETG resin products include, for example, Eastar GN-001, Eastar GN-071, and Eastar 6763, all of which are trade names of Eastman Chemical Company, U.S.A. Commercially available PCT resin products include, for example, Eastar DN-001, Kodar Thermex 6761, Eastar AN-004, and Tritan TX1501HF, all of which are trade names of Eastman Chemical Company, U.S.A.

[0026] The amorphous polyester resin (B) may be composed only of glycol-modified polyethylene terephthalate (b1), but may also contain amorphous polyethylene terephthalate (b2) in addition to (b1).

[0027] Amorphous polyethylene terephthalate (b2) refers to polyethylene terephthalate other than glycol-modified polyethylene terephthalate, which is highly transparent and substantially free of a crystalline structure. The amorphous polyethylene terephthalate can be produced by rapid cooling to facilitate the development of a crystalline structure. Amorphous polyethylene terephthalate is generally known as A-PET. Furthermore, recycled polyethylene terephthalate recovered from PET bottles and the like may also be used as (b2).

[0028] The content of glycol-modified polyethylene terephthalate (b1) in the total amount of the amorphous polyester resin (B) is 15 to 100% by weight or more. If the content of glycol-modified polyethylene terephthalate (b1) is less than 15% by weight, good impact resistance and / or flame retardancy may not be achieved. From the viewpoint of impact resistance and / or flame retardancy, the content of glycol-modified polyethylene terephthalate (b1) is preferably 30% by weight or more, more preferably 40% by weight or more, more preferably 50% by weight or more, even more preferably 70% by weight or more, and particularly preferably 80% by weight or more.

[0029] <Core-shell type elastic body (C)> The resin composition according to the present disclosure contains a core-shell type elastic body (C). Thereby, good impact resistance can be achieved.

[0030] The core-shell elastomer (C) may be composed of polymer particles that are graft copolymers. The core-shell elastomer (C) preferably comprises a shell layer and one or more core layers. The shell layer refers to a polymer layer located on the surface side of the polymer particle and is also called a graft layer. The core layer refers to a polymer layer located more inwardly of the polymer particle than the shell layer and is composed of a rubbery polymer. The core layer may consist of only one layer, or may consist of two or more layers with different monomer compositions. The shell layer covers the surface of the core layer, but is not limited to covering the entire surface of the core layer, as long as it covers at least a portion of the surface of the core layer.

[0031] (Core Layer) The core layer is composed of a rubbery polymer. The rubbery polymer preferably contains at least one selected from the group consisting of natural rubber, diene rubber, acrylate rubber, and polyorganosiloxane rubber, and more preferably contains at least one selected from the group consisting of diene rubber, acrylate rubber, and polyorganosiloxane rubber.

[0032] (Diene Rubber) The diene rubber is an elastomer containing a constituent unit derived from a diene monomer as a constituent unit. The core layer more preferably contains a diene rubber, and particularly preferably is a diene rubber, because the glass transition temperature of the resulting elastomer can be lowered, the impact resistance of the resulting molded article of the polycarbonate resin composition is improved, and the raw material cost is low.

[0033] Examples of the diene monomer include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2-chloro-1,3-butadiene, etc. These diene monomers may be used alone or in combination of two or more.

[0034] The diene rubber may further contain, as a structural unit, a structural unit derived from a vinyl monomer other than the diene monomer that is copolymerizable with the diene monomer.

[0035] Examples of vinyl monomers other than diene monomers copolymerizable with diene monomers (hereinafter also referred to as vinyl monomer A) include: (a) aromatic vinyl monomers such as styrene, α-methylstyrene, monochlorostyrene, and dichlorostyrene; (b) vinylcarboxylic acids such as acrylic acid and methacrylic acid; (c) alkyl (meth)acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate; (d) methacrylic acid, alkyl acrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; (e) hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate; (f) glycidyl group-containing vinyl monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (g) unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile; (h) vinyl acetate; (i) alkenes such as ethylene, propylene, butylene, and isobutylene. The above-mentioned vinyl monomer A may be used alone or in combination of two or more.

[0036] There are no particular limitations on the content of constituent units derived from vinyl monomer A in the diene rubber. The diene rubber preferably contains 50 to 100% by weight of constituent units derived from diene monomers and 0 to 50% by weight of constituent units derived from vinyl monomer A, based on 100% by weight of constituent units.

[0037] The diene rubber may further contain, as a structural unit, a structural unit derived from a polyfunctional monomer such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, etc. In other words, these polyfunctional monomers may be used in the polymerization of the diene rubber.

[0038] Suitable examples of diene rubbers include butadiene rubber (polybutadiene rubber), styrene / butadiene copolymer rubber (poly(styrene / butadiene) rubber), poly(acrylonitrile / butadiene) rubber, butadiene / acrylic acid ester copolymer, etc. Butadiene rubber is an elastomer containing 50 to 100% by weight of structural units derived from 1,3-butadiene, out of 100% by weight of structural units.

[0039] The diene rubber is preferably a butadiene rubber containing 50 to 100% by weight of structural units derived from 1,3-butadiene and 0 to 50% by weight of structural units derived from vinyl monomer A, and more preferably a 1,3-butadiene homopolymer containing 100% by weight of structural units derived from 1,3-butadiene.

[0040] The core layer preferably contains butadiene rubber or styrene / butadiene copolymer rubber because it can lower the glass transition temperature of the resulting elastomer, it can achieve good flame retardancy in the resulting polycarbonate resin composition, it has a high effect of improving impact resistance, and the raw material cost is low.

[0041] (Acrylate-Based Rubber) The acrylate-based rubber is an elastic material containing, as a constituent unit, a constituent unit derived from a (meth)acrylate-based monomer.

[0042] Examples of the (meth)acrylate monomer include: (a) alkyl (meth)acrylate esters having an alkyl group having 1 to 22 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; (b) aromatic ring-containing (meth)acrylate esters, such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; (c) hydroxyalkyl (meth)acrylate esters, such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; (d) glycidyl group-containing (meth)acrylate esters, such as glycidyl (meth)acrylate and glycidyl alkyl (meth)acrylate; and (e) alkoxyalkyl (meth)acrylate esters. These (meth)acrylate monomers may be used alone or in combination of two or more.

[0043] The acrylate rubber may further contain, as a structural unit, a structural unit derived from a vinyl monomer other than the (meth)acrylate monomer that is copolymerizable with the (meth)acrylate monomer. Examples of the vinyl monomer other than the (meth)acrylate monomer that is copolymerizable with the (meth)acrylate monomer include (a) the diene monomers described above, and (b) monomers of the vinyl monomer A other than the (meth)acrylate monomer.

[0044] The acrylic rubber has a crosslinked structure. To introduce the crosslinked structure, for example, a crosslinking agent and / or a graft crosslinking agent can be used when synthesizing the core layer polymer by polymerizing the monomer components. Examples of crosslinking agents and graft crosslinking agents include: (a) allyl alkyl (meth)acrylates such as allyl (meth)acrylate and allyl alkyl (meth)acrylate; (b) polyfunctional (meth)acrylates such as monoethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate; and (c) polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. These crosslinking agents and graft crosslinking agents may be used alone or in combination of two or more.

[0045] Suitable examples of acrylate rubbers include polybutyl acrylate rubber and butyl acrylate / 2-ethylhexyl acrylate copolymer rubber. Polybutyl acrylate rubber is an elastomer containing 50 to 100% by weight of structural units derived from butyl acrylate, based on 100% by weight of structural units.

[0046] Suitable examples of the polyorganosiloxane rubber include silicone rubber and silicone / acrylate rubber.

[0047] Examples of silicone rubbers include polymethylsilicone rubber and polymethylphenylsilicone rubber, etc. Examples of silicone / acrylate rubbers include polyorganosiloxane / butyl acrylate copolymers, etc.

[0048] In one embodiment, the core layer preferably contains one or more materials selected from the group consisting of butadiene rubber, styrene / butadiene copolymer rubber, acrylate rubber, and silicone rubber, and from the viewpoints of improving impact resistance and cost, it is more preferable that the core layer contains butadiene rubber or styrene / butadiene copolymer rubber.

[0049] The weight proportion of the core layer in the entire core-shell type elastomer (C) is preferably 50 to 99% by weight, more preferably 60 to 95% by weight, and even more preferably 70 to 90% by weight, from the viewpoint of compatibility between the core-shell type elastomer (C) and the polycarbonate resin, and from the viewpoint of improving impact resistance.

[0050] (Shell Layer) The shell layer is preferably formed from a polymer containing a structural unit derived from a vinyl monomer, such as an aromatic vinyl compound, a vinyl cyanide compound, an unsaturated carboxylic acid ester, an acrylamide monomer, or a maleimide monomer.

[0051] Suitable examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, and dibromostyrene.

[0052] Suitable examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, and ethacrylonitrile.

[0053] Suitable examples of the unsaturated carboxylic acid ester include: (a) alkyl acrylates having an alkyl group having 1 to 22 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, and behenyl acrylate; (b) alkyl methacrylates having an alkyl group having 1 to 22 carbon atoms, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, and behenyl methacrylate; and (c) alkoxyalkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms and an alkoxyl group, such as methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and ethoxyethyl (meth)acrylate.

[0054] Suitable examples of the acrylamide monomer include acrylamide, methacrylamide, and N-methylacrylamide.

[0055] Suitable examples of the maleimide monomer include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide.

[0056] The polymer constituting the shell layer preferably contains at least one member selected from the group consisting of methyl methacrylate, styrene, and butyl acrylate as a constituent monomer. Note that these may be used alone or in combination of two or more.

[0057] The polymer constituting the shell layer may further contain, as a constituent monomer, at least one reactive vinyl monomer selected from the group consisting of a carboxyl group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer, and a glycidyl group-containing vinyl monomer. By including the reactive vinyl monomer as a constituent monomer in the shell layer, the core-shell elastomer (C) can be made reactive with the polycarbonate resin. As a result, the dispersibility of the core-shell elastomer (C) in the polycarbonate resin is improved, thereby enhancing the impact resistance. Among the reactive vinyl monomers, carboxyl group-containing vinyl monomers are preferred because of their particularly good reactivity with the polycarbonate resin. The reactive vinyl monomers may be used alone or in combination of two or more.

[0058] Suitable examples of the carboxyl group-containing vinyl monomer include acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, isocrotonic acid, vinyloxyacetic acid, allyloxyacetic acid, 2-(meth)acryloylpropanoic acid, 3-(meth)acryloylbutanoic acid, 4-vinylbenzoic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, etc. Among these, acrylic acid and / or methacrylic acid are preferred, and methacrylic acid is more preferred.

[0059] Suitable examples of the hydroxyl group-containing vinyl monomer include (meth)acrylic acid hydroxyalkyl esters having an alkyl group having 1 to 22 carbon atoms and a hydroxyl group, such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0060] Suitable examples of the glycidyl group-containing vinyl monomer include glycidyl (meth)acrylate.

[0061] The amount of the reactive vinyl monomer used can be appropriately set depending on the desired effect and is not particularly limited. When the reactive vinyl monomer is a carboxyl group-containing vinyl monomer, the proportion of the carboxyl group-containing vinyl monomer in the entire polymer particles that are the core-shell type elastomer (C) may be, for example, 0.01 to 5% by weight.

[0062] The weight proportion of the shell layer in the entire core-shell type elastic body (C) is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and even more preferably 10 to 30% by weight, from the viewpoint of compatibility between the core-shell type elastic body (C) and the polycarbonate resin and the effect of improving impact resistance.

[0063] [Particle diameter of core-shell elastomer (C)] The volume average particle diameter of the core-shell elastomer (C) as polymer particles is 100 nm or more from the viewpoint of improving impact resistance. Since larger particle diameters tend to improve impact resistance, the volume average particle diameter is preferably 120 nm or more, more preferably 150 nm or more, even more preferably 200 nm or more, and particularly preferably 250 nm or more. On the other hand, since larger particle diameters of the polymer particles tend to increase the time required for the polymerization reaction and reduce productivity, the volume average particle diameter is preferably 700 nm or less, more preferably 500 nm or less. The volume average particle diameter of the polymer particles is a value measured using a particle diameter measuring device in the state of the polymer particles in a latex state, as shown in the Examples section. The volume average particle diameter of the polymer particles can also be calculated from transmission electron microscope (TEM) images of the polycarbonate resin composition. The particle size of the polymer particles can be controlled by the types and amounts of the polymerization initiator, chain transfer agent, oxidation-reduction agent, emulsifier, etc., the polymerization temperature, the polymerization time, etc.

[0064] [Method for producing the core-shell type elastomer (C)] The method for producing the core-shell type elastomer (C) can be a conventional method and is not particularly limited. For example, any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be adopted, but emulsion polymerization, i.e., emulsion graft polymerization, is preferred. In emulsion graft polymerization, specifically, first, a latex of particles corresponding to the core layer is produced by emulsion polymerization, and then monomer components for the shell layer, a polymerization initiator, etc. are added to the latex to polymerize the monomer components.

[0065] As the emulsifier used in the emulsion polymerization method, it is preferable to use a phosphoric acid emulsifier or a sulfonic acid emulsifier, since this can suppress decomposition of the polycarbonate resin and improve the impact resistance and / or flame retardancy of the resin composition. Specific examples of phosphoric acid emulsifiers or sulfonic acid emulsifiers include alkyl sulfate ester salts, alkyl benzene sulfonates, and alkyl phosphate ester salts. These may be used alone or in combination of two or more. By using a phosphoric acid emulsifier or a sulfonic acid emulsifier during the production of the core-shell type elastomer (C), the resulting core-shell type elastomer (C) may contain a phosphoric acid emulsifier or a sulfonic acid emulsifier.

[0066] Ethylenediaminetetraacetic acid disodium salt, sodium formaldehyde sulfoxylate, ferrous sulfate, etc. may be used as a cocatalyst for polymerization, sodium sulfate, etc. may be used as a latex viscosity modifier, and sodium hydroxide, etc. may be used as a pH adjuster.

[0067] Examples of radical initiators that can be used in emulsion polymerization include organic hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, and t-butyl peroxylaurate; redox initiators that combine an oxidizing agent such as the organic hydroperoxides with a reducing agent such as sulfite, hydrogen sulfite, thiosulfate, first metal salt, and sodium formaldehyde sulfoxylate; persulfates such as potassium persulfate and ammonium persulfate; azo compounds such as azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, and 2-carbamoylazaisobutyronitrile; and organic peroxides such as benzoyl peroxide and lauroyl peroxide. Of these, the radical initiator is preferably an organic hydroperoxide, and more preferably t-butyl hydroperoxide.

[0068] Examples of chain transfer agents used in emulsion polymerization include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, and t-tetradecyl mercaptan; hydrocarbon salts such as tetraethylthiuram sulfide, carbon tetrachloride, ethylene bromide, and pentanephenylethane; terpenes, acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycol, and α-methylstyrene dimer. Among these, the chain transfer agent is preferably a mercaptan, and more preferably t-dodecyl mercaptan. These may be used alone or in combination of two or more.

[0069] The polymerization time may vary depending on the monomer, emulsifier, radical initiator, and chain transfer agent used as needed, and the amounts thereof, but may be, for example, 1 hour to 50 hours, and preferably 5 hours to 24 hours.

[0070] The polymerization temperature can be adjusted depending on the monomers, emulsifier, radical initiator, and chain transfer agent used as needed, and the amounts thereof, and may be, for example, 10°C to 90°C, and preferably 40°C to 80°C.

[0071] Next, the obtained latex containing the core-shell type elastomer (C) may be powdered by, for example, a coagulation method. When powdering the core-shell type elastomer (C), a method of treating the latex obtained by the emulsion polymerization method with a coagulation method such as salt coagulation or acid coagulation, or a method of spray-drying the latex to obtain a powder, can be used. In a coagulation method such as salt coagulation or acid coagulation, the latex may be brought into contact with a coagulant such as an inorganic salt (preferably a divalent inorganic salt, more preferably calcium chloride) or an acid. After coagulation, the core-shell type elastomer (C) may be prepared by further performing heat treatment, dehydration, washing, drying, etc.

[0072] A known method for efficiently producing a core-shell type elastomer (C) having a relatively large particle size by a conventional emulsion polymerization method is to add a water-soluble electrolyte or an acid group-containing copolymer latex to enlarge the particles before or during graft polymerization. Methods for enlarging the particles using a water-soluble electrolyte are disclosed in JP-A-4-170458 and JP-A-60-192754, among others. Methods for enlarging the particles using an acid group-containing copolymer latex are disclosed in JP-A-10-245468 and JP-A-8-12704, among others. Such enlarged core-shell type elastomers can also be used in the present embodiment, and in particular, core-shell type elastomers enlarged using an acid group-containing copolymer latex, i.e., acid latex-enlarged products, can be preferably used.

[0073] Examples of commercially available products of the core-shell type elastomer (C) include Kane Ace (registered trademark) M724 (manufactured by Kaneka Corporation) and Kane Ace (registered trademark) M711 (manufactured by Kaneka Corporation).

[0074] [Amount of Core-Shell Elastomer (C)] The amount of core-shell elastomer (C) in the polycarbonate resin composition according to this embodiment is 1 to 30 parts by weight per 100 parts by weight of the total of the polycarbonate resin (A) and the amorphous polyester resin (B). When the amount of core-shell elastomer (C) is within this range, a polycarbonate resin composition having a good balance of impact resistance, flame retardancy, and fluidity when melted can be provided. The amount is preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight.

[0075] <Flame retardant (D)> The polycarbonate resin composition according to the present disclosure contains a flame retardant. By blending the flame retardant (D) together with the amorphous polyester resin (B), the flame retardancy of the polycarbonate resin composition can be significantly improved.

[0076] As the flame retardant, various flame retardants known to be blended into thermoplastic resins can be used, including, but not limited to, flame retardants described in "Technology and Applications of Polymer Flame Retardation" (pp. 149-221) published by CMC Publishing.

[0077] Particularly, examples of the flame retardants include halogen-based flame retardants such as bromine-based flame retardants such as tetrabromobisphenol A and decabromodiphenyl oxide, and chlorine-based flame retardants such as chlorinated paraffin and chlorinated polyethylene; phosphorus-based flame retardants such as non-halogen phosphate ester-based flame retardants (monophosphate / condensation), halogen-containing phosphate ester-based flame retardants (monophosphate / condensation), inorganic phosphate-based flame retardants, and red phosphorus-based flame retardants; inorganic flame retardants such as antimony trioxide, aluminum hydroxide, and magnesium hydroxide; organic salt-based flame retardants, silicone-based flame retardants, etc. These may be used alone or in combination of two or more.

[0078] Preferred flame retardants include halogenated bisphenol A, halogenated polycarbonate oligomers, and polycarbonate-type flame retardants of halogenated bisphenol A; halogenated flame retardants comprising a combination of a halogen compound such as a brominated epoxy compound and a flame retardant aid such as antimony oxide; organic salt-based flame retardants; phosphorus-based flame retardants such as aromatic phosphate ester-based flame retardants and halogenated aromatic phosphate ester-based flame retardants; and silicone-based flame retardants such as organopolysiloxanes, including branched phenyl silicone compounds and phenyl silicone resins.

[0079] Examples of the halogenated bisphenol A polycarbonate flame retardant include tetrabromobisphenol A polycarbonate flame retardants, and copolymer polycarbonate flame retardants of tetrabromobisphenol A and bisphenol A.

[0080] Examples of the organic salt-based flame retardant include dipotassium diphenylsulfone-3,3'-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, potassium 2,4,5-trichlorobenzenesulfonate, potassium bis(2,6-dibromo-4-cumylphenyl)phosphate, sodium bis(4-cumylphenyl)phosphate, potassium bis(p-toluenesulfone)imide, potassium bis(diphenylphosphate)imide, potassium bis(2,4,6-tribromophenyl)phosphate, potassium bis(2,4-dibromophenyl)phosphate, potassium bis(4-bromophenyl)phosphate, potassium diphenylphosphate, sodium diphenylphosphate, potassium perfluorobutanesulfonate, sodium or potassium lauryl sulfate, and sodium or potassium hexadecyl sulfate.

[0081] Examples of the halogenated aromatic phosphate ester type flame retardants include tris(2,4,6-tribromophenyl)phosphate, tris(2,4-dibromophenyl)phosphate, and tris(4-bromophenyl)phosphate.

[0082] Examples of the aromatic phosphate ester-based flame retardant include triphenyl phosphate, tris(2,6-xylyl)phosphate, tetrakis(2,6-xylyl)resorcinol diphosphate, tetrakis(2,6-xylyl)hydroquinone diphosphate, tetrakis(2,6-xylyl)-4,4'-biphenol diphosphate, tetraphenylresorcinol diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4'-biphenol diphosphate, an aromatic polyphosphate in which the aromatic ring source is resorcinol and phenol and does not contain a phenolic hydroxyl group (OH group), an aromatic polyphosphate in which the aromatic ring source is resorcinol and phenol and contains a phenolic OH group, an aromatic polyphosphate in which the aromatic ring source is hydroquinone and phenol and does not contain a phenolic OH group, and an aromatic polyphosphate in which the aromatic ring source is hydroquinone and phenol and does not contain a phenolic OH group. Examples of aromatic polyphosphates include aromatic polyphosphates which are hydroquinone and phenol and contain a phenolic OH group (hereinafter, "aromatic polyphosphate" refers to both aromatic polyphosphates containing and not containing a phenolic OH group), aromatic polyphosphates whose aromatic ring sources are bisphenol A and phenol, aromatic polyphosphates whose aromatic ring sources are tetrabromobisphenol A and phenol, aromatic polyphosphates whose aromatic ring sources are resorcinol and 2,6-xylenol, aromatic polyphosphates whose aromatic ring sources are hydroquinone and 2,6-xylenol, aromatic polyphosphates whose aromatic ring sources are bisphenol A and 2,6-xylenol, and aromatic polyphosphates whose aromatic ring sources are tetrabromobisphenol A and 2,6-xylenol.

[0083] From the viewpoint of achieving both good flame retardancy and impact resistance, the blending amount of the flame retardant (D) is preferably 1 to 80 parts by weight, more preferably 5 to 60 parts by weight, and particularly preferably 10 to 40 parts by weight, per 100 parts by weight of the total of the polycarbonate-based resin (A) and the amorphous polyester-based resin (B). The polycarbonate-based resin composition according to this embodiment can have improved flame retardancy compared to conventional compositions, making it possible to reduce the blending amount of the flame retardant. Furthermore, by reducing the blending amount of the flame retardant, further improvement in impact resistance can be expected.

[0084] <Anti-Drip Agent> The polycarbonate-based resin composition according to this embodiment may be blended with an anti-drip agent to prevent melt dripping during combustion. Examples of the anti-drip agent include fluoroolefin-based resins containing a fluoroolefin resin as a main component. Fluoroolefin resins are polymers, copolymers, or composites containing a fluoroethylene structure. Examples of fluoroolefin resins include difluoroethylene polymers, tetrafluoroethylene polymers, tetrafluoroethylene-hexafluoropropylene copolymers, copolymers of tetrafluoroethylene and fluorine-free ethylene-based monomers, and composites of tetrafluoroethylene polymers and vinyl-based resins such as acrylic resins. Of these, polytetrafluoroethylene (PTFE) is preferred. The weight-average molecular weight of polytetrafluoroethylene is preferably 500,000 or more, and particularly preferably 500,000 to 10,000,000.

[0085] Among polytetrafluoroethylenes, compounds having fibril-forming ability are preferred because they can impart even higher melt-dripping prevention properties. Examples of polytetrafluoroethylenes having fibril-forming ability include compounds classified as Type 3 in the ASTM standard. Examples of polytetrafluoroethylenes classified as Type 3 include Teflon (registered trademark) 6-J (manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201 (manufactured by Daikin Industries, Ltd.), CD1, CD076 (manufactured by Asahi ICI Fluoropolymers Co., Ltd.), and the like.

[0086] Examples of polytetrafluoroethylenes other than compounds classified as Type 3 include Algoflon F5 (manufactured by Montefluos Co., Ltd.), Polyflon MPA, and Polyflon FA-100 (manufactured by Daikin Industries, Ltd.) These polytetrafluoroethylenes may be used alone or in combination of two or more types.

[0087] From the viewpoint of achieving both prevention of melt dripping during combustion and impact resistance, the blending amount of the anti-drip agent is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, per 100 parts by weight of the polycarbonate-based resin (A) and the amorphous polyester-based resin (B). The blending amount of the anti-drip agent can be appropriately determined depending on the level of flame retardancy required for the molded article, for example, UL94 V-0, V-1, V-2, etc., and also taking into consideration the blending amounts of other components, etc.

[0088] <Other resins> The polycarbonate resin composition according to the present embodiment may or may not contain thermoplastic resins other than the polycarbonate resin (A) and the amorphous polyester resin (B).

[0089] The polycarbonate-based resin composition according to this embodiment may contain a crystalline polyester-based resin in addition to the amorphous polyester-based resin (B), but from the viewpoint of achieving good impact resistance and flame retardancy, the content is preferably small. Specifically, the content of the crystalline polyester-based resin is preferably 0 to 15 parts by weight, more preferably 0 to 10 parts by weight, and even more preferably 0 to 5 parts by weight, per 100 parts by weight of the total of the polycarbonate-based resin (A) and the amorphous polyester-based resin (B). Alternatively, it may be 0 to 1 part by weight, or 0 to 0.1 part by weight.

[0090] The definition of the crystalline polyester resin is as described above, and specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, and the like.

[0091] When the polycarbonate-based resin composition according to this embodiment contains a thermoplastic resin other than the polycarbonate-based resin (A), the amorphous polyester-based resin (B), and the crystalline polyester-based resin, the thermoplastic resin is not particularly limited, but examples thereof include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polytetrafluoroethylene, ABS resin, AS resin, acrylic resin, polyacetal, modified polyphenylene ether, polyamide, cyclic polyolefin, etc. The amount of the other thermoplastic resin is not particularly limited, but is, for example, 0 to 100 parts by weight, preferably 0 to 50 parts by weight, more preferably 0 to 30 parts by weight, even more preferably 0 to 10 parts by weight, and particularly preferably 0 to 5 parts by weight, per 100 parts by weight of the total of the polycarbonate-based resin (A) and the amorphous polyester-based resin (B).

[0092] <Other Additives> The polycarbonate resin composition according to this embodiment may contain, as appropriate, additives that can be blended into general thermoplastic resin compositions. Such additives are not particularly limited, but examples thereof include reinforcing materials, fillers, antioxidants, pigments, dyes, conductivity-imparting agents, hydrolysis inhibitors, thickeners, plasticizers, lubricants, UV absorbers, antistatic agents, flow improvers, release agents, compatibilizers, and heat stabilizers.

[0093] <Method for producing resin composition> The method for producing the polycarbonate-based resin composition according to this embodiment is not particularly limited, and known methods can be used. For example, the polycarbonate-based resin composition can be produced by a known method of blending and melt-kneading the components using an apparatus such as a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a two-roll mill, a kneader, or a Brabender. In order to suppress yellowing of the resin composition due to thermal degradation of the polycarbonate-based resin, it is preferable that the melt-kneading temperature be as low as possible.

[0094] <Molded Articles and Applications> The polycarbonate-based resin composition according to this embodiment can be molded into a predetermined shape to form a molded article. Specifically, the polycarbonate-based resin composition can be extruded to form, for example, extruded articles having various shapes, extrusion-molded sheets, films, and the like. Examples of extrusion molding methods include cold runner and hot runner molding methods, as well as injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluids), insert molding, in-mold coating molding, adiabatic mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding. Sheet or film molding can also be achieved by inflation, calendaring, casting, or the like. Furthermore, a specific stretching operation can be performed to form a heat-shrinkable tube. Hollow molded articles can also be obtained by rotational molding, blow molding, or the like.

[0095] Molded articles made from the polycarbonate-based resin composition according to this embodiment can be used in a wide range of applications, such as various housings, hard-coated products, glazing materials, light diffusion plates, optical disk substrates, light guide plates, medical materials, and miscellaneous goods. Specifically, the resin can be used as resin products formed into, for example, exterior materials for office automation equipment and home appliances, various containers, miscellaneous goods, such as exterior materials for personal computers, notebook computers, game consoles, display devices (CRT, LCD, plasma, projectors, organic EL, etc.), mice, printers, copiers, scanners, and fax machines (including multifunction devices thereof), keyboard keys, molded switch products, personal digital assistants (so-called PDAs), mobile phones, portable books (dictionaries, etc.), portable televisions, drives for recording media (CDs, MDs, DVDs, Blu-ray discs, hard disks, etc.), readers for recording media (IC cards, smart media, memory sticks, etc.), optical cameras, digital cameras, parabolic antennas, power tools, VTRs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, lighting equipment, refrigerators, air conditioners, air purifiers, negative ion generators, and typewriters. The product may also be a tray, a cup, a plate, a shampoo bottle, an office equipment housing, a cosmetic bottle, a beverage bottle, an oil container, an injection-molded product (golf tee, a cotton swab core, a candy stick, a brush, a toothbrush, a helmet, a syringe, a plate, a cup, a comb, a razor handle, a tape cassette and case, a disposable spoon or fork, stationery such as a ballpoint pen, etc.), etc.

[0096] The molded article may also be used in the form of binding tape (binding band), prepaid cards, balloons, pantyhose, hair caps, sponges, cellophane tape, umbrellas, raincoats, plastic gloves, hair caps, ropes, tubes, foam trays, foam cushioning materials, cushioning materials, packaging materials, cigarette filters, and the like.

[0097] Furthermore, the molded article may be a vehicle part such as a lamp socket, a lamp reflector, a lamp housing, an instrument panel, a center console panel, a deflector part, a car navigation part, a car audiovisual part, or an automobile mobile computer part.

[0098] The following items list preferred aspects of the present disclosure, but the present invention is not limited to the following items. [Item 1] A composition comprising a polycarbonate resin (A), an amorphous polyester resin (B), a core-shell elastomer (C), and a flame retardant (D), wherein the content of the amorphous polyester resin (B) is 15 to 35% by weight of the total of the polycarbonate resin (A) and the amorphous polyester resin (B), the amorphous polyester resin (B) contains a glycol-modified polyethylene terephthalate (b1), and the content of the glycol-modified polyethylene terephthalate (b1) in the amorphous polyester resin (B) is 15 to 100% by weight, the content of the core-shell elastomer (C) is 1 to 30 parts by weight per 100 parts by weight of the total of the polycarbonate resin (A) and the amorphous polyester resin (B), and the volume average particle diameter of the core-shell elastomer (C) is 100 nm or more, A resin composition, wherein the core-shell elastomer (C) contains a phosphoric acid-based emulsifier or a sulfonic acid-based emulsifier as an emulsifier. [Item 2] The resin composition according to Item 1, wherein the core-shell elastomer (C) has a core layer containing butadiene rubber or styrene / butadiene copolymer rubber, and a shell layer containing a polymer containing at least one monomer selected from the group consisting of methyl methacrylate, styrene, and butyl acrylate as a constituent monomer. [Item 3] The resin composition according to Item 1 or 2, wherein the content of the glycol-modified polyethylene terephthalate (b1) in the amorphous polyester resin (B) is 40 to 100 wt %. [Item 4] The resin composition according to any one of Items 1 to 3, wherein the core-shell elastomer (C) is an acid latex-enlarged product. [Item 5] A molded article obtained by molding the resin composition according to any one of Items 1 to 4.

[0099] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0100] <Volume Average Particle Diameter of Core-Shell Elastomer> The volume average particle diameter of the core-shell elastomer in a latex state was measured using a particle size analyzer (Nanotracwave, manufactured by Nikkiso Co., Ltd.) by light scattering at a wavelength of 546 nm.

[0101] <Production Example 1> <Preparation of Polybutadiene Rubber Latex> A 100-liter pressure-resistant polymerization vessel was charged with 200 parts of pure water, 0.002 parts of ethylenediaminetetraacetic acid disodium salt, 0.0012 parts of ferrous sulfate, 1.5 parts of polyoxyethylene alkyl ether sodium phosphate, and 0.5 parts of t-dodecyl mercaptan. After deacidification, 100 parts of butadiene, 0.05 parts of sodium formaldehyde sulfoxylate, and 0.2 parts of paramenthane hydroperoxide were added, and the reaction solution was maintained at pH 6.5 to 7.5 at 50°C for 20 hours to obtain a diene rubber latex (1a) with a conversion of 98 wt% and a volume average particle size of 80 nm. <Preparation of Acid Group-Containing Latex> An 8-liter polymerization vessel was charged with 200 parts of water and 0.5 parts of dioctyl sodium sulfosuccinate, and the temperature was raised to 70°C while stirring and flowing nitrogen. 0.3 parts of sodium formaldehyde sulfoxylate, 0.0025 parts of ferrous sulfate, and 0.01 parts of ethylenediaminetetraacetic acid were added, and after several minutes, a mixture of 2 parts of butyl methacrylate, 23 parts of butyl acrylate, 2 parts of methacrylic acid, 0.125 parts of t-dodecyl mercaptan, and 0.025 parts of cumene hydroperoxide was continuously added dropwise at a rate of 20 parts / hour using a metering pump. After the addition of the mixture, a mixture of 58 parts of butyl methacrylate, 2 parts of butyl acrylate, 13 parts of methacrylic acid, 0.3 parts of t-dodecyl mercaptan, and 0.08 parts of cumene hydroperoxide was added dropwise at a rate of 20 parts / hour. Polymerization was terminated 1.5 hours after the completion of the dropwise addition. The conversion was 99.7%, the volume average particle size was 120 nm, the concentration was 33%, and the pH was 2.8. <Preparation of Polybutadiene-Enlarged Rubber Latex> 100 parts (solids content) of the polybutadiene rubber latex obtained above and 20 parts of water were placed in an 8-liter polymerization vessel, and the temperature was raised to 60°C while stirring and flowing nitrogen. 0.1 parts of sodium hydroxide and 2.4 parts (solids content) of the acid group-containing latex obtained above were added, and stirring was continued for 1 hour to expand the polybutadiene. 200 parts of water and 0.4 parts of polyoxyethylene alkyl ether sodium phosphate were added, and stirring was continued for an additional 30 minutes to complete the expansion. A polybutadiene-enlarged rubber latex with a volume average particle size of 270 nm was obtained.<Graft Copolymerization of Polybutadiene-Enlarged Rubber> 75 parts (solids equivalent) of the polybutadiene-enlarged rubber latex obtained above was charged into an 8-liter polymerization vessel and heated to 60°C while stirring and flowing nitrogen. 0.18 parts of sodium formaldehyde sulfoxylate, 0.001 parts of ferrous sulfate, and 0.004 parts of ethylenediaminetetraacetic acid were added, and 0.2 parts of t-butyl hydroperoxide was added to a graft monomer mixture (8 parts styrene, 17 parts methyl methacrylate) and continuously added dropwise at a rate of 10 parts / hour using a metering pump. After the addition of the monomer mixture was completed, stirring was continued for an additional hour to complete the polymerization. The polymerization conversion was 96%, and the volume average particle size of the latex was 300 nm. To the latex, 0.5 parts each of dilauryl-3,3'-thiodipropionate and 2,6-di-t-butyl-4-methylphenol were added, and then 5 parts of calcium chloride were added to cause salting out. After heat treatment at 90°C, the mixture was dehydrated and dried to obtain a resin powder of a core-shell type elastomer (C-3).

[0102] <Production Example 2> <Preparation of Polybutadiene Rubber Latex> 200 parts of water, 0.2 parts of potassium persulfate, and 0.2 parts of t-dodecyl mercaptan were placed in a 100-liter pressure polymerization vessel and stirred. After thorough nitrogen substitution to remove oxygen, 1 part of sodium oleate, 2 parts of sodium rosinate, and 100 parts of butadiene were added to the system, and the temperature was raised to 60°C to initiate polymerization. The polymerization was completed in 12 hours. The conversion rate was 96%, and the volume average particle size of the rubber latex was 70 nm. <Preparation of Acid Group-Containing Latex> 200 parts of water and 0.5 parts of sodium dioctyl sulfosuccinate were placed in an 8-liter polymerization vessel and the temperature was raised to 70°C while stirring and flowing nitrogen. 0.3 parts of sodium formaldehyde sulfoxylate, 0.0025 parts of ferrous sulfate, and 0.01 parts of ethylenediaminetetraacetic acid were added, and after several minutes, a mixture of 2 parts of butyl methacrylate, 23 parts of butyl acrylate, 2 parts of methacrylic acid, 0.125 parts of t-dodecyl mercaptan, and 0.025 parts of cumene hydroperoxide was continuously added dropwise at a rate of 20 parts / hour using a metering pump. After the addition of the mixture, a mixture of 58 parts of butyl methacrylate, 2 parts of butyl acrylate, 13 parts of methacrylic acid, 0.3 parts of t-dodecyl mercaptan, and 0.08 parts of cumene hydroperoxide was added dropwise at a rate of 20 parts / hour. Polymerization was terminated 1.5 hours after the completion of the dropwise addition. The conversion was 99.7%, the volume average particle size was 120 nm, the concentration was 33%, and the pH was 2.8. <Preparation of Polybutadiene-Enlarged Rubber Latex> 100 parts (solids equivalent) of the polybutadiene rubber latex obtained above and 20 parts of water were placed in an 8-liter polymerization vessel, and the temperature was raised to 60°C while stirring and flowing nitrogen. 0.1 parts of sodium hydroxide and 2.0 parts (solids equivalent) of the acid group-containing latex obtained above were added, and stirring was continued for 1 hour to allow the polybutadiene to expand. 200 parts of water and 0.4 parts of sodium dodecylbenzenesulfonate were added, and stirring was continued for an additional 30 minutes to complete the expansion. A polybutadiene-enlarged rubber latex with a volume average particle diameter of 350 nm was obtained. <Graft Copolymerization of Polybutadiene-Enlarged Rubber> 70 parts (solids equivalent) of the polybutadiene-enlarged rubber latex obtained above was placed in an 8-liter polymerization vessel, and the temperature was raised to 60°C while stirring and flowing nitrogen.0.18 parts of sodium formaldehyde sulfoxylate, 0.001 parts of ferrous sulfate, and 0.004 parts of ethylenediaminetetraacetic acid were added, and 0.2 parts of t-butyl hydroperoxide was added to a graft monomer mixture (8 parts of styrene, 22 parts of methyl methacrylate) and continuously added dropwise at a rate of 10 parts / hour using a metering pump. To maintain the stability of the latex during the addition of the monomer mixture, 0.2 parts of dioctyl sodium sulfosuccinate was added four times at hourly intervals. After the completion of the addition of the monomer mixture, stirring was continued for another hour to complete the polymerization. The polymerization conversion was 96%, and the volume average particle size of the latex was 350 nm. To the latex, 0.5 parts each of dilauryl-3,3'-thiodipropionate and 2,6-di-t-butyl-4-methylphenol were added, and then 5 parts of calcium chloride were added to cause salting out. After heat treatment at 90°C, the mixture was dehydrated and dried to obtain a resin powder of a core-shell type elastomer (C'-3).

[0103] Examples 1 to 7 and Comparative Examples 1 to 7 Pellets and test pieces composed of a resin composition containing a polycarbonate resin were prepared using the components shown below according to the formulations shown in Table 1, and the Charpy strength (impact strength), tensile properties, flexural properties, HDT, flame retardancy, and MFR were measured. Note that MFR is an index of fluidity when melted. A higher MFR value indicates higher fluidity when melted.

[0104] Component (A): Polycarbonate resin (Panlite L-1225WP, manufactured by Teijin Limited), blending amount (wt%) shown in Table 1

[0105] Component (B): amorphous polyester resin, blending amount (wt%) shown in Table 1 b1-1: glycol-modified polyethylene terephthalate (Eastman Chemical Company, Eastar GN-001) b1-2: glycol-modified polyethylene terephthalate (Eastman Chemical Company, Tritan TX1501HF) b2-1: amorphous polyethylene terephthalate (Teijin Limited, TRN-MTJ)

[0106] Component (B'): Comparative resin, blending amount (wt%) shown in Table 1 B'-1: ABS resin (AF3510, manufactured by FCFC Corporation) B'-2: Acrylonitrile-styrene resin (SAN-R, manufactured by Techno Polymer Co., Ltd.)

[0107] Component (C) or (C'): core-shell type elastomer, blending amount shown in Table 1 [parts by weight relative to 100 parts by weight of the total of components (A) and (B) or (B')] C-1: Kane Ace M724, manufactured by Kaneka Corporation, volume average particle size 120 nm, contains a phosphoric acid-based emulsifier C-2: Kane Ace M711, manufactured by Kaneka Corporation, volume average particle size 200 nm, contains a sulfonic acid-based emulsifier C-3: Core-shell type elastomer (C-3) manufactured in Production Example 1, volume average particle size 300 nm, contains a phosphoric acid-based emulsifier C'-1: Kane Ace B513, manufactured by Kaneka Corporation, volume average particle size 75 nm, contains a fatty acid-based emulsifier C'-2: Kane Ace M701, manufactured by Kaneka Corporation, volume average particle size 210 nm, contains a fatty acid-based emulsifier C'-3: Core-shell type elastomer (C'-3) produced in Production Example 2, volume average particle diameter 350 nm, containing a fatty acid-based emulsifier

[0108] Component (D): flame retardant (aromatic condensed phosphate ester, PX200 manufactured by Daihachi Chemical Industry Co., Ltd.), blended amount shown in Table 1 [parts by weight per 100 parts by weight of the total of components (A) and (B) or (B′)]

[0109] Other additives: Anti-drip agent: PTFE G355 manufactured by Asahi Glass Co., Ltd., 0.1 part by weight per 100 parts by weight of the total of components (A) and (B) or (B'). Stabilizer: Adekastab 2112 and Adekastab AO-60 manufactured by ADEKA Corporation, 0.1 part by weight per 100 parts by weight of the total of components (A) and (B) or (B').

[0110] (Conditions for preparing pellets and test pieces) A ​​mixture of the components was kneaded and extruded at a screw rotation speed of 100 rpm in a twin-screw extruder (TEX44SS manufactured by The Japan Steel Works, Ltd.) heated to a barrel temperature of 230 to 260°C. The pellets were dried in a dryer at 100°C for 12 hours to sufficiently reduce the moisture content, and then test pieces were prepared in an injection molding machine (FAS100B manufactured by Fanuc Corporation) at a molding temperature of 270 to 290°C and a mold temperature of 50°C.

[0111] (Charpy Strength) The Charpy impact strength of the test piece with a length of 63.5 mm, a width of 12.7 mm, and a thickness of 3.2 mm, and having a V-notch, prepared by the method described above, was measured at −30° C. and 23° C. by a method conforming to the ASTM D6110 standard.

[0112] (Tensile Properties) The ASTM D638-1 type test piece having a thickness of 3.2 mm prepared by the above-mentioned method was measured for yield strength and elongation at break in an absolute dry state at 23°C at a test speed of 50 mm / min by a method in accordance with the ASTM D638 standard.

[0113] (Flexural Properties) In accordance with ASTM D-0790, flexural strength and flexural modulus were measured using a ¼ inch bar at a test speed of 5 mm / min, at 23° C., and with a support distance of 100 mm.

[0114] (HDT) A test piece having a length of 127 mm, a width of 12.7 mm and a thickness of 6.4 mm, prepared by the method described above, was annealed at 60°C for 2 hours, and then subjected to a test of 18.6 kgf / cm by a method conforming to ASTM D648 standard. ２ The HDT (deflection temperature under load) was measured at a load of 1000 kJ / cm.

[0115] (Flame Retardancy) The pellets prepared under the above conditions were dried at 100°C for 8 hours, and then injection molded using an injection molding machine (TOYO (100i), clamping pressure: 100 tons) under conditions of a cylinder setting temperature of 235°C to 260°C and a mold temperature of 50°C to obtain test pieces measuring 127 mm x 12.7 mm x 1.2 mm thick. The resulting bar-shaped test pieces with a thickness of 1.2 mm were used to evaluate flammability in accordance with the UL94 Standard V test.

[0116] (MFR) The MFR value of the pellets prepared under the above conditions was measured in accordance with JIS K7210 Method A at a measurement temperature of 250° C. and a load of 5 kg. The results of the above measurements are shown in Table 1.

[0117]

[0118] The following can be seen from Table 1: The polycarbonate resin compositions of the examples each exhibited good values ​​for impact resistance, flame retardancy, and fluidity when melted, and the balance of the physical properties was good.

[0119] On the other hand, Comparative Example 1, which does not contain amorphous polyester resin (B) but instead contains a general ABS resin, and Comparative Example 2, which does not contain amorphous polyester resin (B) but instead contains a general acrylonitrile-styrene resin, are found to have insufficient flame retardancy. Comparative Example 3, which contains amorphous polyester resin (B) but at a high content, is also found to have insufficient flame retardancy. Comparative Example 4, which does not contain glycol-modified polyethylene terephthalate (b1) as the amorphous polyester resin (B) but only contains amorphous polyethylene terephthalate (b2), is found to have low impact resistance, insufficient flame retardancy, a small MFR value, and insufficient fluidity when melted. Comparative Examples 5 to 7, which use a core-shell elastomer that does not contain a phosphoric acid-based emulsifier or a sulfonic acid-based emulsifier, are found to have insufficient flame retardancy.

Claims

1. Polycarbonate-based resin (A), Amorphous polyester resin (B), A core-shell type elastic body (C), and Contains a flame retardant (D), the content of the amorphous polyester resin (B) is 15 to 35% by weight based on the total weight of the polycarbonate resin (A) and the amorphous polyester resin (B); The amorphous polyester resin (B) contains a glycol-modified polyethylene terephthalate (b1), the content of the glycol-modified polyethylene terephthalate (b1) in the amorphous polyester resin (B) is 15 to 100% by weight, the content of the core-shell type elastomer (C) is 1 to 30 parts by weight per 100 parts by weight of the total of the polycarbonate-based resin (A) and the amorphous polyester-based resin (B), The core-shell type elastic body (C) has a volume average particle size of 250 nm or more, The core-shell type elastomer (C) comprises a phosphoric acid-based emulsifier as an emulsifier in the resin composition.

2. The resin composition according to claim 1, wherein the core-shell type elastomer (C) has a core layer containing butadiene rubber or a styrene / butadiene copolymer rubber, and a shell layer containing a polymer containing at least one selected from the group consisting of methyl methacrylate, styrene, and butyl acrylate as a constituent monomer.

3. The resin composition according to claim 1 or 2, wherein the content of the glycol-modified polyethylene terephthalate (b1) in the amorphous polyester resin (B) is 40 to 100% by weight.

4. 3. The resin composition according to claim 1, wherein the core-shell type elastomer (C) is an acid latex-enlarged product.

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

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