JP5255407B2 - Flame retardant thermoplastic resin composition and molded article comprising the same - Google Patents

Description

  The present invention relates to a flame retardant thermoplastic resin composition excellent in flame retardancy, heat resistance, mechanical strength, and transparency, and a molded product thereof.

  Conventionally, styrene-based resins that have been given flame retardancy have a good balance of molding processability, good mechanical properties, and are excellent in electrical insulation. It is used in.

  Generally, for the purpose of imparting a design to a resin product, the product may be fully painted or partially painted. However, the coating process tends to reduce the production yield due to poor coating. Also, from the flow of emission control of volatile organic compounds (VOC), it is possible to color it in a vivid color or deep color without giving a coating treatment as much as possible, or to give it a metallic or pearly appearance. Thus, a resin that easily imparts design properties has been desired.

  As a method for making a styrene resin flame retardant, a method of adding a phosphorus flame retardant having a specific structure (for example, see Patent Documents 1 and 2) has been proposed. However, no mention is made of the design properties of the resulting composition.

In addition, a method of adding a phosphate ester flame retardant to a rubber-reinforced styrene resin copolymerized with an unsaturated carboxylic acid alkyl ester (for example, see Patent Documents 3 to 7), a method of adding a halogen flame retardant (for example, a patent) Reference 8) is excellent in design including colorability because it has transparency, but a large amount of flame retardant is required to impart flame retardancy, so heat resistance and impact strength are not sufficient. There wasn't.
JP 59-24736 A JP 7-26093 A JP 2000-344994 A JP 2001-200131 A JP 2002-201330 A JP 2002-206039 A JP 2003-201384 A JP 62-116648 A

  As described above, it was difficult to simultaneously exhibit flame retardancy, heat resistance, mechanical strength, and transparency.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the problem can be solved by adding a specific amount of an aromatic polycarbonate resin (D) having a specific range of molecular weight. Reached.

  That is, the present invention is as follows.

[1] A graft copolymer (A) obtained by graft-polymerizing an aromatic vinyl monomer and one or more monomers copolymerizable therewith to a rubbery polymer, an aromatic vinyl monomer Copolymer (B) obtained by copolymerizing a monomer and one or more monomers copolymerizable therewith, a methyl methacrylate monomer and one or two or more monomers copolymerizable therewith A flame retardant (F) 5 to 50 parts by mass is added to 100 parts by mass of a copolymer (C) obtained by copolymerizing monomers and a thermoplastic resin composition (E) comprising an aromatic polycarbonate resin (D). A flame retardant thermoplastic resin composition comprising a weight average molecular weight Mw of the aromatic polycarbonate resin (D) and the aromatic polycarbonate resin (D) in the thermoplastic resin composition (E). The relationship of the content G (% by mass) is expressed by the following formulas (1) and (2 The flame retardant thermoplastic resin composition characterized by satisfying.
13,000 ≦ Mw ≦ 30,000 (1)
1 ≦ G ≦ −2.9 × 10 ⁻⁴ × Mw + 20.824 (2)

[2] A copolymer (B) obtained by copolymerizing an aromatic vinyl monomer and one or more monomers copolymerizable therewith, a methyl methacrylate monomer, and a copolymer thereof 100 parts by mass of a thermoplastic resin composition (E) comprising a copolymer (C) obtained by copolymerizing one or two or more possible monomers and an aromatic polycarbonate resin (D), a flame retardant (F And 5-50 parts by mass of a flame retardant thermoplastic resin composition comprising a weight average molecular weight Mw of the aromatic polycarbonate resin (D) and the thermoplastic resin composition (E). The flame retardant thermoplastic resin composition, wherein the relationship of the content G (% by mass) of the aromatic polycarbonate resin (D) satisfies the formulas (1) and (2).
13,000 ≦ Mw ≦ 30,000 (1)
1 ≦ G ≦ −2.9 × 10 ⁻⁴ × Mw + 20.824 (2)

[3] The flame retardant thermoplastic resin composition according to [1], wherein the rubbery polymer in the graft copolymer (A) is a conjugated diene rubber.

[4] The flame retardant thermoplastic resin composition according to [1] or [2], wherein the flame retardant (F) is a phosphate ester flame retardant represented by the following general formula (1).

(R ^a , R ^b , R ^c , and R ^d are each an independent aryl group, and one or more hydrogens thereof may or may not be substituted. N is a natural number, and X is a divalent phenol. (The aromatic groups derived from j, k, l, and m are each independently 0 or 1.)

[5] The flame-retardant thermoplastic resin composition according to [1] or [2], wherein the content of the copolymer (C) in the thermoplastic resin composition (E) is 30 to 90% by mass. .

[6] The flame retardant thermoplastic resin composition according to [1] or [2], wherein the content of the methyl methacrylate monomer in the copolymer (C) is 60 to 99.5% by mass.

[7] A molded article comprising the flame retardant thermoplastic resin composition according to any one of [1] to [6].

  According to the present invention, it is possible to obtain a thermoplastic resin composition and a molded product excellent in the balance of flame retardancy, heat resistance, mechanical strength, and transparency.

  The rubbery polymer used for the graft copolymer (A) in the present invention includes polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylic copolymer, styrene-butadiene-styrene block copolymer. Polymers, polyisoprene, styrene-isoprene copolymers, conjugated diene rubbers such as styrene-isoprene-butadiene copolymers, and hydrogenated products thereof, acrylic rubbers such as ethyl acrylate and butyl acrylate, ethylene- An α-olefin-polyene copolymer, an ethylene-α-olefin copolymer, a silicone rubber, a silicone-acrylic rubber and the like can be mentioned, and these can be used alone or in combination of two or more. Among these, polybutadiene, polyisoprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acrylic copolymer, acrylic rubber, ethylene-α-olefin-polyene copolymer, ethylene- α-olefin copolymer, silicone rubber, silicone-acrylic rubber, particularly preferred are polybutadiene, polyisoprene, butadiene-styrene copolymer, styrene-isoprene copolymer, styrene-isoprene-butadiene copolymer, These are a butadiene-acrylonitrile copolymer and a butadiene-acrylic copolymer, and by using these, a thermoplastic resin composition and a molded product particularly excellent in mechanical strength and transparency can be obtained.

  Examples of the aromatic vinyl monomer in the graft copolymer (A) and the copolymer (B) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, and pt-butyl. Styrene and vinyl naphthalene are mentioned, and these can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are particularly preferable.

  In the graft copolymer (A) and copolymer (B), examples of the monomer copolymerizable with the aromatic vinyl monomer include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, acrylic Acrylic acid esters such as methyl acid, ethyl acrylate and butyl acrylate, methacrylic acid esters of the same substitution, acrylic acids such as acrylic acid and methacrylic acid, and N such as N-phenylmaleimide and N-methylmaleimide -Substituted maleimide monomers, glycidyl group-containing monomers such as glycidyl methacrylate, etc., among which acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, N -Phenylmaleimide, glycidyl methacrylate.

  In the graft copolymer (A), the content of the aromatic vinyl monomer in the component excluding the rubbery polymer is preferably 60 to 90% by mass, more preferably 65 to 85% by mass, particularly preferably. Is 70 to 85% by mass, most preferably 75 to 85% by mass. When the content of the aromatic vinyl monomer is within this range, a composition having particularly excellent transparency can be obtained. In the present invention, the volume average particle size of the rubbery polymer in the graft copolymer (A) is preferably 0.1 to 1.2 μm, more preferably from the balance of mechanical strength, molding processability, and appearance of the molded product. Is 0.15 to 0.8 μm, more preferably 0.15 to 0.6 μm, and particularly preferably 0.2 to 0.4 μm.

  Moreover, the graft ratio in a graft copolymer (A) becomes like this. Preferably it is 10-150 mass%, More preferably, it is 20-110 mass%, More preferably, it is 25-60 mass%. By setting the graft ratio within this range, a composition having excellent mechanical strength and good moldability can be obtained. The graft ratio is defined as the weight ratio of the monomer graft-polymerized to the rubber polymer to the rubber polymer. The measuring method is as follows. The polymer produced by the polymerization reaction is dissolved in acetone and separated into an acetone-soluble component and an insoluble component by a centrifuge. At this time, the component dissolved in acetone is a component that has not undergone a graft reaction (non-graft component) in the copolymer that has undergone a polymerization reaction, and the acetone insoluble component is a component that has undergone a graft reaction to the rubber polymer and the rubber polymer. (Graft component). Since the value obtained by subtracting the weight of the rubbery polymer from the weight of the acetone-insoluble component is defined as the weight of the graft component, the graft ratio can be determined from these values.

  The refractive index of the rubber polymer is preferably 1.51 to 1.54 as the refractive index at 20 ° C. When the refractive index is within this range, a composition having particularly excellent transparency can be obtained.

  The reduced viscosity (ηsp / c) of the copolymer (B) is preferably 0.3 to 1.0 dl / g, more preferably 0.35 to 1.0 dl / g, still more preferably 0.35 to 0.8 dl / g, particularly preferably 0.40 to 0.8 dl / g. When the reduced viscosity is within this range, a composition excellent in impact resistance and flame retardancy can be obtained. The reduced viscosity is obtained by measuring the outflow time in a Cannon-Fenske type capillary at 30 ° C. with respect to a solution obtained by dissolving 0.50 g of the copolymer (B) in 100 ml of 2-butanone.

  Monomers that can be copolymerized with the methyl methacrylate monomer in the copolymer (C) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, ethylstyrene, and pt-butylstyrene. , Aromatic vinyl monomers such as vinyl naphthalene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth ) N-butyl acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxy (meth) acrylate Propyl, (meth) acrylic acid 2,3,4,5,6-pentahydroxyhexyl and (meth) acrylic acid 2,3 Unsaturated carboxylic acid alkyl ester monomers such as 4,5-tetra-hydroxypentyl and the like, which may be used alone or in combination of two or more. Among these, styrene, acrylonitrile, and methyl acrylate are preferable, and methyl acrylate is particularly preferable.

  The content of the methyl methacrylate monomer in the copolymer (C) is preferably 60 to 99.5% by mass, more preferably 68 to 99.5% by mass, and further preferably 80 to 99.5% by mass. Most preferably, it is 90 to 98% by mass. When the methyl methacrylate monomer is within this range, a composition having not only excellent flame retardancy and transparency but also excellent scratch resistance can be obtained.

  The reduced viscosity of the copolymer (C) is preferably 0.18 to 0.8 ml / g, more preferably 0.20 to 0.8 ml / g, still more preferably 0.25 to 0.80 ml. / G, particularly preferably 0.30 to 0.65 ml / g. When the reduced viscosity is within this range, a composition excellent in impact resistance and flame retardancy can be obtained. The reduced viscosity is measured by measuring the outflow time in a Cannon-Fenske type capillary at 30 ° C. for a solution obtained by dissolving 0.50 g of the copolymer (C) in 100 ml of 2-butanone in the same manner as the copolymer (B). Can be obtained.

  The graft copolymer (A), copolymer (B), and copolymer (C) are produced by a known method such as emulsion polymerization, bulk polymerization, suspension polymerization, suspension bulk polymerization, or solution polymerization. Can do.

  The content of the copolymer (C) in the thermoplastic resin composition (E) is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, particularly preferably 40 to 80% by mass, Most preferably, it is 40-70 mass%. When the content of the copolymer (C) is within this range, a composition not only excellent in flame retardancy, mechanical strength and transparency, but also excellent in scratch resistance can be obtained.

  As the aromatic polycarbonate resin (D), those produced by a known method can be used. Specifically, a known method of reacting an aromatic dihydroxy compound and a carbonate precursor, for example, reacting an aromatic dihydroxy compound and a carbonate precursor (for example, phosgene) in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent. Crystallized carbonate prepolymer obtained by interfacial polymerization method (for example, phosgene method), transesterification method (melting method) in which aromatic dihydroxy compound and carbonic acid diester (for example, diphenyl carbonate) are reacted, phosgene method or melting method Polymerization methods (Japanese Patent Laid-Open No. 1-158033 (corresponding to US Pat. No. 4,948,871), Japanese Patent Laid-Open No. 1-271426, Japanese Patent Laid-Open No. 3-68627 (corresponding to US Pat. No. 5,204,377)), etc. What was manufactured by the method can be used.

  The measurement of the weight average molecular weight (Mw) of aromatic polycarbonate resin can be performed using gel permeation chromatography (GPC), and the measurement conditions are as follows.

That is, it is obtained by using a converted molecular weight calibration curve according to the following formula from the composition curve of standard monodisperse polystyrene using polystyrene gel with tetrahydrofuran as a solvent.
M _pc = 0.3591 M _ps ^1.0388
(M _pc is the molecular weight of aromatic polycarbonate resin, M _ps is the molecular weight of polystyrene)

  Moreover, the aromatic polycarbonate resin can also be used in combination of 2 or more types of aromatic polycarbonate resins having different molecular weights.

The relationship between the weight average molecular weight Mw and the content G (mass%) of the aromatic polycarbonate resin (D) in the thermoplastic resin composition (E) satisfies the formulas (1) and (2), and the point ABCD in FIG. A hatched portion (including a boundary line) surrounded by, preferably a portion surrounded by a point AEFD satisfying the expressions (1) and (3), more preferably a point GEFH satisfying the expressions (1) and (4) It is the part surrounded by.
13,000 ≦ Mw ≦ 30,000 (1)
1 ≦ G ≦ −2.9 × 10 ⁻⁴ × Mw + 20.824 (2)
4 ≦ G ≦ −2.9 × 10 ⁻⁴ × Mw + 20.824 (3)
4 ≦ G ≦ −2.9 × 10 ⁻⁴ × Mw + 17.824 (4)

  When this is in this range, a composition excellent in flame retardancy, particularly flame retardancy in a moisture absorption state, heat resistance, mechanical strength, and transparency can be obtained.

  The flame retardant (F) means a known compound that is liquid or solid at room temperature and can be imparted with flame retardancy by adding to a resin. For example, an organic phosphorus compound, red phosphorus, inorganic phosphoric acid Examples thereof include phosphorus-based salts such as salts, halogen-based, silica-based, and silicone-based flame retardants.

  Examples of organic phosphorus compounds include phosphate ester compounds and condensed phosphate ester compounds such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl. Phosphate esters such as phosphate, tricresyl phosphate, trixylenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, compounds obtained by modifying these with various substituents, or tris (chloroethyl) ) Phosphate, bis (2,3 dibromopropyl) 2,3-dichloropropyl phosphate, tris (dichloro) Propyl) phosphate, bis (chloropropyl) monooctyl phosphate, etc., include halogen-containing acid ester and, preferable among them, phosphoric acid ester compound, and a condensed phosphoric acid ester compound.

Among these, the condensed phosphate ester compound represented by the following general formula (1) is particularly preferable.

(R ^a , R ^b , R ^c, and R ^d are each independently an aryl group, and one or more hydrogens thereof may or may not be substituted. N is a natural number, and X is a divalent phenol. Aromatic groups derived from the class, j, k, l and m are each independently 0 or 1.)

Of these, the condensed phosphate compound represented by the following general formula (2) is most preferable.

  By using the flame retardant represented by the formula (2), a composition particularly excellent in the balance of flame retardancy, mechanical strength, heat resistance, and design properties can be obtained.

  As red phosphorus, in addition to general red phosphorus, the surface thereof is coated with a metal hydroxide film selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide in advance, Coated with a coating made of a metal hydroxide selected from aluminum oxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide and a thermosetting resin, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, hydroxide Examples thereof include a double coating treatment with a thermosetting resin film on a metal hydroxide film selected from titanium.

  Examples of the inorganic phosphate include ammonium polyphosphate.

  Examples of the halogen flame retardant include aromatic halogen compounds, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenylene ethers, halogenated polyphenylene thioethers, and halogenated alkyl triazine compounds, preferably bromo. Bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate resin, brominated polystyrene resin, brominated polystyrene resin, brominated bisphenol cyanurate resin, brominated polyphenylene oxide, polydibromophenylene oxide, decabromo Diphenyl oxide bisphenol condensates (tetrabromobisphenol A, oligomers thereof, etc.), brominated alkyltriazine compounds, etc. It is below.

  These can be used alone or in combination of two or more.

  The addition amount of the flame retardant (F) is 5 to 50 parts by mass, preferably 10 to 30 parts by mass, and more preferably 10 to 25 parts by mass with respect to 100 parts by mass of the thermoplastic resin composition (E). When the added amount of the flame retardant (F) is within this range, a composition excellent in flame retardancy, heat resistance and mechanical strength can be obtained.

  Although there is no restriction | limiting in particular in the mixing method of the flame-retardant resin composition (E) in this invention, A well-known melt mixing method can be used. Specific examples include batch kneaders such as mixing rolls, Banbury mixers, and pressure kneaders, and continuous kneaders such as single screw extruders and twin screw extruders.

  The order of kneading is not particularly limited. For example, a method of kneading all of the materials at once, a method of producing a masterbatch containing a high concentration of flame retardant (F) or aromatic polycarbonate resin (D), and then diluting The most preferable is graft copolymer (A) / copolymer (B) / copolymer (C) / aromatic polycarbonate resin (D), or graft copolymer (A) / In this method, a masterbatch containing a high concentration of the aromatic polycarbonate resin (D) is produced by a combination of copolymer (C) / aromatic polycarbonate resin (D), and then the remaining resin and the flame retardant are melt mixed. By this method, a composition excellent in flame retardancy, mechanical strength, and transparency can be obtained.

  It is preferable that the total light transmittance in 23 degreeC in the 2.5 mm thickness flat plate of the flame-retardant thermoplastic resin composition of this invention is 60% or more, More preferably, it is 70% or more. Further, the haze is preferably less than 40%, more preferably less than 30, and still more preferably less than 25. When these are in this range, coloring to a bright color or a deep color is possible, and a molded product excellent in design can be obtained.

  As a method for controlling the total light transmittance within this range, for example, the refractive index of the rubbery polymer and the refractive index of the component comprising the copolymer (B) and the copolymer (C) are 1.51 to 1.54. In the case where the component comprising the copolymer (B) and the copolymer (C) has a LSCT type cloud point curve, molding at a temperature below the cloud point, and melt kneading. In this case, there may be mentioned a method performed under the condition that the aromatic polycarbonate resin (D) is dispersed with a smaller dispersed particle diameter. For the molding of the present invention, a known method generally used for molding a thermoplastic resin, for example, injection molding, injection compression molding, extrusion molding, blow molding, inflation molding, vacuum molding, press molding, or the like is used. Can do.

  In particular, in injection molding, if the cavity surface temperature immediately before the resin is filled into the mold cavity is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, transferability to the cavity surface is improved, and design properties are further improved. Can be obtained. In general, when the cavity surface temperature is increased, the time until cooling becomes longer, so there is a problem that the molding cycle becomes longer, but by using a heat cycle molding method in which the cavity surface is heated and cooled in a short time, the design property is improved. Both improvement and productivity can be achieved.

  In the present invention, known additives such as plasticizers, lubricants (for example, higher fatty acids and their metal salts, higher fatty acid amides, etc.), heat stabilizers, antioxidants (for example, phenols) are used depending on the purpose. Type, phosphite type, thiodibropropionic acid ester type thioether, etc.), weathering agent (for example, benzotriazole type, benzophenone type, salicylate type, cyanoacrylate type, oxalic acid derivative, hindered amine type, etc.), flame retardant aid ( For example, antimony trioxide, antimony pentoxide, etc.), antistatic agent (for example, polyamide elastomer, quaternary ammonium salt, pyridine derivative, aliphatic sulfonate, aromatic sulfonate, aromatic sulfonate copolymer) , Sulfate ester salt, polyhydric alcohol partial ester, alkyldiethanolamine, alkyldie Noramide, polyalkylene glycol derivatives, betaines, imidazoline derivatives, etc.), antibacterial agents, antifungal agents, slidability improvers (for example, hydrocarbons such as low molecular weight polyethylene, higher alcohols, polyhydric alcohols, polyglycols, poly Glycerol, higher fatty acid, higher fatty acid metal salt, fatty acid amide, ester of fatty acid and aliphatic alcohol, full ester or partial ester of fatty acid and polyhydric alcohol, full ester or partial ester of fatty acid and polyglycol, silicone type, Fluorine resin system etc.) can be blended at an arbitrary ratio according to the purpose.

  For the purpose of imparting design properties, known colorants such as inorganic pigments, organic pigments, metallic pigments and dyes can be added.

  Examples of inorganic pigments include titanium oxide, carbon black, titanium yellow, iron oxide pigments, ultramarine blue, cobalt blue, chromium oxide, spinel green, lead chromate pigments, and cadmium pigments.

  Examples of organic pigments include azo pigments such as azo lake pigments, benzimidazolone pigments, diarylide pigments, and condensed azo pigments, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, isoindolinone pigments, quinophthalone pigments, quinacridone pigments, and perylene pigments. And condensed polycyclic pigments such as anthraquinone pigment, perinone pigment, and dioxazine violet.

  Examples of metallic pigments include flake-like aluminum metallic pigments, spherical aluminum pigments used to improve the weld appearance, mica powder for pearl-like metallic pigments, and other polyhedral particles of inorganic substances such as glass. Are coated with plating or sputtering.

  Examples of dyes include nitroso dyes, nitro dyes, azo dyes, stilbene azo dyes, ketoimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine / polymethine dyes, thiazole dyes, indamine / indophenol dyes, azines Examples thereof include dyes, oxazine dyes, thiazine dyes, sulfur dyes, amino ketone / oxyketone dyes, anthraquinone dyes, indigoid dyes, and phthalocyanine dyes.

  These colorants can be used alone or in combination of two or more.

  Hereinafter, the present invention will be specifically described with reference to examples. Moreover, the evaluation in an Example was performed in accordance with the following method.

(1) Notched Charpy impact strength (kJ / m ² )
Evaluation was performed according to ISO179.

(2) Flexural modulus (MPa)
Evaluation was performed according to ISO178.

(3) Deflection temperature under load (1.8 MPa load) (° C)
Evaluation was performed according to ISO75-1,2.

(4) Melt volume flow rate According to ISO1133, it evaluated at 220 degreeC and the load 98N.

(5) Total light transmittance (%), haze (%)
Using an injection molding machine, a flat plate having a size of 5 cm × 9 cm and a thickness of 2.5 mm was injection molded at a cylinder temperature = 220 ° C. and a mold temperature = 60 ° C. Using this flat plate, evaluation was performed according to ASTM D1003.

(6) Flame retardancy Evaluated according to UL-94. (Thickness 1.6mm)
Aging condition: The test piece was treated at 70 ° C. × 168 hours, then cooled in a desiccator containing silica gel for 4 hours or more, and then a combustion test was performed.
Acceptance state (flame retardant property of moisture absorption state): The test piece was left in an atmosphere of 23 ° C. and 50% humidity for 30 days, and then a combustion test was performed.
Judgment was good (◯) only when both the aging condition and the acceptance state were passed, and was judged as bad (x) if either one failed.

(Reference Example 1) Production of polybutadiene rubber latex 950 parts by weight of butadiene monomer, 50 parts by weight of acrylonitrile, 135 parts by weight of deionized water (iron concentration: less than 0.02 ppm), 3.0 parts by weight of potassium oleate, 0 parts of potassium persulfate .3 parts by mass, 0.2 parts by mass of terrestrial decyl mercaptan and 0.18 parts by mass of potassium hydroxide were placed in a pressure vessel equipped with a stirrer, and the temperature was raised to 70 ° C. to initiate polymerization. A polybutadiene latex having a volume average particle size of 80 nm and a solid content of 40% by mass measured with a Microtrac particle size analyzer “nanotrac 150” (trade name) manufactured by Nikkiso Co., Ltd. was obtained in a polymerization time of 15 hours. This is an emulsifier

Was added in an amount of 0.1 parts by mass with respect to 100 parts by mass of the solid content of the latex, and after stirring for 5 minutes, 0.65 parts by mass of acetic acid was added. Next, 0.65 parts by mass of potassium hydroxide was added to obtain a stable latex. This latex was a latex having a particle size distribution with a volume average particle size of 250 nm, was not a coagulum, and was a highly concentrated agglomerated latex having a solid content of 37% by mass. The mass fraction of latex having a particle diameter of 350 nm or more was 11% by mass.

(Reference Example 2) Production of Graft Copolymer (A) To 135 parts by mass of the polybutadiene rubber latex produced in Reference Example 1, 0.1 part by mass of tertiary lead decyl mercaptan and deionized water (iron concentration: less than 0.02 ppm) ) 15 parts by mass, the gas phase part was replaced with nitrogen, 25 parts by mass of deionized water, 0.06 parts by mass of sodium formaldehyde sulfoxylate, 0.0008 parts by mass of ferrous sulfate, disodium ethylenediaminetetraacetate After adding an aqueous solution in which 0.02 part by mass of salt was dissolved, the temperature was raised to 55 ° C. Subsequently, while the temperature was raised to 70 ° C. over 1.5 hours, a single unit consisting of 10 parts by mass of acrylonitrile, 40 parts by mass of styrene, 0.4 parts by mass of terleaded decyl mercaptan, and 0.15 parts by mass of cumene hydroperoxide. An aqueous solution prepared by dissolving 0.035 parts by mass of sodium formaldehyde sulfoxylate in 25 parts by mass of demerized water and deionized water was added over 4 hours. After completion of the addition, 0.02 part by mass of cumene hydroperoxide was added, and then the polymerization reaction was completed for 1 hour while controlling the reaction vessel at 70 ° C.

  After adding a silicone resin defoamer and a phenolic antioxidant emulsion to the ABS latex thus obtained, adjust the solid content concentration by adding deionized water to 10% by mass, After heating to 70 ° C., an aqueous aluminum sulfate solution was added for solidification, and solid-liquid separation was performed with a screw press. The water content at this time was 10% by mass. This was dried to obtain a graft copolymer (A).

  The composition ratio of the copolymer was 9.7% by mass of acrylonitrile and 51.3% by mass of butadiene as a result of composition analysis using a Fourier transform infrared spectrophotometer (FR-IR) (manufactured by JASCO Corporation). The styrene content was 39.0% by mass. The graft ratio was 46% by mass, and the reduced viscosity (0.50 g / 100 ml, measured at 30 ° C. in 2-butanone solution) of the non-grafted component (acetone soluble component) was 0.31 dl / g.

Reference Example 3 Production of Copolymer (B) In the method described in Example 1 of Japanese Patent No. 19605311, acrylonitrile and styrene were used as a solvent, and secondary butyl alcohol was used as a solvent, and the above mixed solution was continuously added to a polymerization reactor. The polymerization reaction was carried out by controlling the temperature of the polymerization meter from 140 to 160 ° C. Thereafter, unreacted monomers were removed under vacuum to obtain a solid powder of copolymer (B). As a result of composition analysis using a Fourier transform infrared spectrophotometer (FR-IR) (manufactured by JASCO Corporation), the composition of the copolymer was 20.8% by mass of acrylonitrile and 79.2% by mass of styrene. there were. The reduced viscosity was 0.75 dl / g.

Reference Example 4 Production of Copolymer (C) To a monomer mixture consisting of 68.6 parts by weight of methyl methacrylate, 1.4 parts by weight of methyl acrylate, and 30 parts by weight of ethylbenzene, 1,1-di-t -0.015 parts by mass of butylperoxy-3,3,5-trimethylcyclohexane and 0.15 parts by mass of n-octyl mercaptan were added and mixed uniformly. This solution is continuously supplied to a sealed pressure resistant reactor having an internal volume of 10 liters, polymerized with stirring at an average temperature of 135 ° C. and an average residence time of 2 hours, and then continuously sent to a storage tank connected to the reactor. Then, it was introduced into a devolatilization apparatus maintained at a high vacuum of 260 ° C. and 10 mmHg, and the unreacted monomer and solvent were devolatilized and recovered, and further transferred to an extruder in a molten state. Here, lauric acid and stearyl alcohol were quantitatively supplied from an additive spout connected to the extruder in a melted state at 90 ° C. to obtain copolymer (C-1) pellets. The reduced viscosity of this copolymer was 0.35 dl / g, and the composition was analyzed using a proton NMR method. As a result, methyl methacrylate unit / methyl acrylate unit = 98.0 / 2.0 (weight ratio). The result was obtained. Furthermore, when lauric acid and stearyl alcohol in the resin composition were quantified, the results were 0.03 and 0.1 parts by mass, respectively, per 100 parts by mass of the resin composition.

Reference Example 5 Aromatic polycarbonate resin (D-1)
A bisphenol A polycarbonate produced from bisphenol A and diphenyl carbonate by a melt transesterification method, and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) as a hindered phenol antioxidant ) One containing 400 ppm propionate and 200 ppm tris (2,4-di-t-butylphenyl) phosphite as a phosphite heat stabilizer.
Weight average molecular weight (Mw) = 15,000
Phenolic end group ratio (ratio of phenolic end groups to the total number of end groups) = 29 mol%

Reference Example 6 Aromatic polycarbonate resin (D-2)
In the same manner as in Reference Example 7, an aromatic polycarbonate resin (D-2) was obtained. The weight average molecular weight (Mw) was 22,000, and the phenolic end group ratio was 25 mol%.

Reference Example 7 Aromatic polycarbonate resin (D-3)
In the same manner as in Reference Example 7, an aromatic polycarbonate resin (D-3) was obtained. The weight average molecular weight (Mw) was 26,000, and the phenolic end group ratio was 25 mol%.

Reference Example 8 Aromatic Polycar and Nate Resin (D-4)
In the same manner as in Reference Example 7, an aromatic polycarbonate resin (D-4) was obtained. The weight average molecular weight (Mw) was 35,000, and the phenolic end group ratio was 27 mol%.

(Flame retardant F)
The following were used as flame retardants.
Flame retardant (F-1): “PX200” manufactured by Daihachi Chemical Co., Ltd.
(1,3-phenylenebis (2,6-dimethylphenyl phosphate))

Flame retardant (F-2): “CR-741” manufactured by Daihachi Chemical Co., Ltd.
α-Diphenoxyphosphoryl-ω-phenoxypoly (n = 1 to 3) [oxy-1,4-phenyleneisopropylidene-1,4-phenyleneoxy (phenoxyphosphoryl)]

Example 1
Graft copolymer (A) 22.5 parts by mass, after removing moisture sufficiently, copolymer (B) 17.5 parts by mass, copolymer (C) 50 parts by mass, aromatic polycarbonate resin ( D-1) After mixing 10 parts by mass, this was charged into a hopper, and while the flame retardant (F-1) was quantitatively charged using a quantitative feeder, a twin screw extruder (PCM-30, L / D = 28, manufactured by Ikekai Tekko Co., Ltd.) and kneaded under conditions of a cylinder setting temperature of 260 ° C., a screw rotation speed of 200 rpm, and a kneaded resin discharge speed of 12 kg / hr to obtain resin pellets, and evaluation of each characteristic Went. The evaluation results are shown in Table 1.

(Example 2)
After mixing 20 parts by weight of the graft copolymer (A), 40 parts by weight of the copolymer (C), and 40 parts by weight of the aromatic polycarbonate resin (D-1) after sufficiently drying and removing water, Using a twin screw extruder (PCM-30, L / D = 28, manufactured by Ikekai Tekko Co., Ltd.), the cylinder is set at a temperature of 270 ° C., the screw speed is 200 rpm, and the kneading resin discharge speed is 20 kg / Master batch pellets were obtained by kneading under the conditions of hr. The master batch pellets, the graft copolymer (A), the copolymer (B), and the copolymer (C) were mixed so as to have the ratio shown in Table 1, and then mixed into a hopper to obtain a flame retardant (F -1) is using a twin screw extruder (PCM-30, L / D = 28, manufactured by Ikekai Tekko Co., Ltd.) while quantitatively using a quantitative feeder. Kneading was performed under the conditions of a rotation speed of 200 rpm and a kneading resin discharge speed of 12 kg / hr to obtain resin pellets, and each characteristic was evaluated. The evaluation results are shown in Table 1.

(Examples 3 and 5-8)
Resin pellets were obtained and evaluated in the same manner as in Example 2. The evaluation results are shown in Table 1.

Example 4
Example 2 except that a flame retardant (F-2) heated to 80 ° C. was press-fitted using a gear pump from the position 2/3 of the screw length from the die tip of the twin-screw extruder and kneaded. Thus, each characteristic was evaluated. The evaluation results are shown in Table 1.

(Comparative Examples 1 and 2)
Resin pellets were obtained and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Examples 3-5)
Resin pellets were obtained and evaluated in the same manner as in Example 2. The evaluation results are shown in Table 1.

  Examples 1 to 8 have flame retardancy and transparency, and are excellent in mechanical property balance.

  On the other hand, Comparative Example 1 is excellent in mechanical property balance and transparency because the aromatic polycarbonate resin (D) is not added, but has insufficient flame retardancy in a hygroscopic state. In Comparative Example 2, the flame retardancy is sufficient by increasing the amount of flame retardant added, but the mechanical property balance is inferior. In Comparative Examples 3 to 5, since the molecular weight or content of the aromatic polycarbonate resin is out of the range surrounded by the point ABCD in FIG. 1, the transparency is not sufficient.

  By using the composition of this invention, the flame-retardant thermoplastic resin composition excellent in the balance of a flame retardance, heat resistance, impact resistance, and transparency, and a molded article can be obtained.

It is a figure which shows the relationship between the weight average molecular weight Mw of aromatic polycarbonate resin (D), and content G (mass%).

Claims (5)

In the graft copolymer (A) in the component excluding the rubber polymer, the rubber polymer having a volume average particle diameter of 0.1 to 1.2 μm and a refractive index of 1.51 to 1.54 at 20 ° C. aromatic vinyl monomer content of 60 to 90% by weight, and copolymerizable therewith one or more kinds of monomers obtained by graft polymerization the graft copolymer (a) A copolymer having a reduced viscosity (ηsp / c) of 0.3 to 1.0 dl / g obtained by copolymerizing an aromatic vinyl monomer and one or more monomers copolymerizable therewith 59-13 mass% in combination with coalescence (B)
A copolymer having a reduced viscosity (ηsp / c) of 0.18 to 0.8 ml / g obtained by copolymerizing a methyl methacrylate monomer and one or more monomers copolymerizable therewith ( 40 ) to 70% by mass of C)
And 100 parts by mass of the thermoplastic resin composition (E) containing the aromatic polycarbonate resin (D), the flame retardant thermoplastic resin composition containing 5 to 50 parts by mass of the flame retardant (F),
The relationship between the weight average molecular weight Mw of the aromatic polycarbonate resin (D) and the content G (% by mass) of the aromatic polycarbonate resin (D) in the thermoplastic resin composition (E) is expressed by the following formula (1). And the said flame-retardant thermoplastic resin composition characterized by satisfying (2).
13,000 ≦ Mw ≦ 30,000 (1)
1 ≦ G ≦ −2.9 × 10 ⁻⁴ × Mw + 20.824 (2)   The flame-retardant thermoplastic resin composition according to claim 1, wherein the rubbery polymer in the graft copolymer (A) is a conjugated diene rubber. The flame retardant thermoplastic resin composition according to claim 1 or 2, wherein the flame retardant (F) is a phosphate ester flame retardant represented by the following general formula (1).

(R ^a , R ^b , R ^c , and R ^d are each an independent aryl group, and one or more hydrogens thereof may or may not be substituted. N is a natural number, and X is a divalent phenol. (The aromatic groups derived from j, k, l, and m are each independently 0 or 1.) The flame-retardant thermoplastic resin composition according to any one of claims 1 to 3, wherein a content of the methyl methacrylate monomer in the copolymer (C) is 60 to 99.5 mass%. The molded article which consists of a flame-retardant thermoplastic resin composition as described in any one of Claims 1-4 .