JP2014009350A - Polyphenylene ether/polycarbonate flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene ether/polycarbonate flame retardant resin composition excellent in high surface appearance and balance of heat-resistance and flame-retardancy, and to provide a molding made of the composition, an automotive lamp extension component, a lighting fitting extension component and a lighting fitting reflector component.SOLUTION: The polyphenylene ether/polycarbonate flame retardant resin composition contains: 100 pts.mass of a polyphenylene ether/polycarbonate resin containing 69-95 mass% of a polyphenylene ether (A) and 5-31 mass% of a polycarbonate (B); 3-10 pts.mass of a phosphoric ester based flame retarder (C); and 0.05-1.0 pt.mass of a flame retarder (D) being a polystyrene and/or acrylonitrile-styrene copolymer introduced with a sulfonic acid group and/or a sulfonate group.

Description

  The present invention relates to a polyphenylene ether / polycarbonate flame-retardant resin composition, and a molded product obtained therefrom, an automotive lamp extension component, a lighting fixture extension component, and a lighting fixture reflector component.

  Home appliances and automobile lamps are mainly composed of a lamp, a reflector that reflects the light from the lamp, an extension around the reflector, an outer cover, and a housing on the back.

  Since the reflector is the closest to the light source, it has the highest heat resistance, and the materials used for these are mainly thermosetting resins such as unsaturated polyester resin, bulk molding compound (BMC), or ultra-high such as polyetherimide. Conventionally, heat-resistant thermoplastic resins or aluminum materials have been widely used.

  Since the extension is slightly away from the light source, the required heat resistance is lower than that of the reflector material. However, a thermoplastic resin such as a high heat-resistant polycarbonate having a relatively high heat resistance is still used.

  In these applications, high molding appearance (surface smoothness) and heat resistance are required, and in recent years, high flame resistance is also being required.

  Polyphenylene ether resins have various properties such as excellent mechanical properties, electrical properties, acid resistance, alkali resistance, and heat resistance, low water absorption, and good dimensional stability. Therefore, if the polyphenylene ether resin composition is made flame retardant and a molded product such as an extension is formed, the molded product has a good surface appearance and brightness feeling, in particular, with sufficient heat resistance, mechanical properties, and good molding fluidity. I can expect.

  However, in products represented by lamp reflectors and extensions, etc., where flame retardancy is required, if flame retarded with conventional flame retardants, the heat resistance of polyphenylene ether resin is greatly reduced, and heat resistance and difficulty Not both flammability and good surface appearance.

  Patent Documents 1 and 2 propose a flame retardant in which a sulfonic acid group and / or a sulfonic acid group are introduced into polystyrene or an acrylonitrile-styrene copolymer (hereinafter also referred to as “AS resin”). Patent Documents 1 and 2 describe that this flame retardant is excellent in compatibility with a resin composition, and that even if the contained resin composition is stored for a long period of time, appearance failure and mechanical strength are unlikely to deteriorate.

JP 2005-272537 A JP 2005-272538 A

  Patent Documents 1 and 2 exemplify a resin composition containing a flame retardant in which a sulfonic acid group and / or a sulfonic acid group are introduced into polystyrene or AS resin. The main resin is a polyphenylene ether resin or two kinds of resins. As the above polymer alloy, polyphenylene ether / polycarbonate alloy (hereinafter also referred to as “PPE / PC”) is exemplified.

  However, even if this flame retardant is simply added to the PPE / PC alloy, the balance between flame retardancy and heat resistance and the surface appearance of the resulting resin composition are not satisfactory. Patent Documents 1 and 2 also describe the combined use of the flame retardant and a conventional phosphoric ester-based flame retardant. However, merely using these flame retardants only satisfies the requirements as a lamp member. A polyphenylene ether / polycarbonate flame-retardant resin composition having a balance between the surface appearance, heat resistance and flame retardancy cannot be obtained.

  The present invention has been made in view of the above problems, and provides a polyphenylene ether / polycarbonate flame retardant resin composition excellent in the balance between high surface appearance, heat resistance and flame retardancy, and further from them. It is an object of the present invention to provide a molded article, an automobile lamp extension part, an extension part for a lighting fixture, and a reflector part for a lighting fixture.

Therefore, the present inventors have intensively studied to solve the above problems. As a result, it comprises a polyphenylene ether and a specific ratio of polycarbonate, a phosphate ester flame retardant, a flame retardant in which a sulfonic acid group and / or a sulfonic acid group is introduced into polystyrene or AS resin (acrylonitrile-styrene copolymer). It has been found that the above-mentioned problems can be solved by a polyphenylene ether / polycarbonate flame-retardant resin composition and a molded product obtained by molding them, and the present invention has been completed.
That is, the present invention is as follows.

[1]
100 parts by mass of polyphenylene ether / polycarbonate resin containing 69 to 95% by mass of polyphenylene ether (A) and 5 to 31% by mass of polycarbonate (B);
3 to 10 parts by mass of phosphate ester flame retardant (C),
A flame retardant (D) 0.05 to 1.0 part by mass, which is a polystyrene and / or acrylonitrile-styrene copolymer into which a sulfonic acid group and / or a sulfonic acid group is introduced,
Polyphenylene ether / polycarbonate flame-retardant resin composition.
[2]
The styrene resin (E) not reinforced with rubber is added in an amount of 0 to 30 masses with respect to 100 mass parts in total of the component (A), the component (B), the component (C), and the component (D). The polyphenylene ether / polycarbonate flame-retardant resin composition according to item [1], further comprising:
[3]
The polyphenylene ether / polycarbonate difficulty according to [2] above, wherein the styrene resin (E) not reinforced with rubber is acrylonitrile-styrene resin having an acrylonitrile unit content of 5 to 15% by mass and / or general-purpose polystyrene. A flammable resin composition.
[4]
The styrenic block copolymer (F) is added in an amount of 0.5 to 10 mass with respect to a total of 100 mass parts of the component (A), the component (B), the component (C), and the component (D). The polyphenylene ether / polycarbonate flame-retardant resin composition according to any one of [1] to [3], further comprising:
[5]
The reduced viscosity of the polyphenylene ether (A) as measured at 30 ° C. using a chloroform solvent is any one of [1] to [4] above, wherein the reduced viscosity is 0.25 to 0.55 dl / g. A polyphenylene ether / polycarbonate flame-retardant resin composition.
[6]
A molded article comprising the polyphenylene ether / polycarbonate flame-retardant resin composition according to any one of [1] to [5] above.
[7]
An automotive lamp extension component comprising the polyphenylene ether / polycarbonate flame-retardant resin composition according to any one of [1] to [5] above.
[8]
An extension part of a lighting fixture comprising the polyphenylene ether / polycarbonate flame-retardant resin composition according to any one of [1] to [5] above.
[9]
A reflector part for a lighting fixture comprising the polyphenylene ether / polycarbonate flame-retardant resin composition according to any one of [1] to [5] above.

  The polyphenylene ether / polycarbonate flame-retardant resin composition of the present invention has a good balance between flame retardancy and heat resistance, and has an appearance of a molded product after aluminum deposition (such as white spots on the surface of the molded product after aluminum deposition). Reduction). The molded body made of the polyphenylene ether / polycarbonate flame-retardant resin composition can be favorably used for lamp extension parts of automobiles, extensions of various lighting fixtures, and reflector parts.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

≪Polyphenylene ether / polycarbonate flame-retardant resin composition≫
The polyphenylene ether / polycarbonate flame-retardant resin composition of this embodiment is
100 parts by mass of polyphenylene ether / polycarbonate resin containing 69 to 95% by mass of polyphenylene ether (A) and 5 to 31% by mass of polycarbonate (B);
3 to 10 parts by mass of phosphate ester flame retardant (C),
The flame retardant (D) 0.05-1.0 mass part which is a polystyrene and / or acrylonitrile-styrene copolymer which introduce | transduced the sulfonic acid group and / or the sulfonate group is included.

  By using the above flame retardant resin composition, it has a balance of excellent flame retardancy, good heat resistance, fluidity and impact resistance, and further, the appearance of the molded body after aluminum deposition An automotive lamp extension molded body excellent in (reduction of white spots on the surface of the molded body after aluminum vapor deposition) and excellent in brightness on the glossy surface of the molded body, and extensions and reflector parts of various lighting fixtures can be obtained. Hereinafter, each component of the above resin composition will be described in detail.

<Polyphenylene ether (A)>
The polyphenylene ether (A) is not particularly limited, but specifically, a homopolymer (homopolymer) or copolymer (a) having [a] and / or [b] of the following formula (1) as a repeating unit: A copolymer).

  In [a] and [b] of the above formula (1), R1, R2, R3, R4, R5, and R6 are each independently an alkyl group having 1 to 4 carbon atoms or an aryl having 6 to 12 carbon atoms. It is preferably a group or a monovalent residue such as halogen and hydrogen. However, the case where R5 and R6 are hydrogen at the same time is excluded. Further, the alkyl group preferably has 1 to 3 carbon atoms, the aryl group has more preferably 6 to 8 carbon atoms, and more preferably hydrogen among the monovalent residues. The number of repeating units in [a] and [b] in (1) is not particularly limited because it varies depending on the molecular weight distribution of the polyphenylene ether (A).

  Although it does not specifically limit as polyphenylene ether (A) of a homopolymer, Specifically, poly (2, 6- dimethyl- 1, 4- phenylene) ether, poly (2-methyl-6-ethyl- 1, 4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-) n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, Poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether and poly (2-methyl-6) Chloroethyl-1,4-phenylene) ether. Among these, poly (2,6-dimethyl-1,4-phenylene) ether is preferable from the viewpoint of easy availability of raw materials and processability.

  Further, the polyphenylene ether (A) of the copolymer is not particularly limited, but specifically, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethyl Examples thereof include those mainly composed of a polyphenylene ether structure, such as a copolymer of phenol and o-cresol and a copolymer of 2,3,6-trimethylphenol and o-cresol. Among these, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable from the viewpoint of easy availability of raw materials and processability, and 2,6-dimethylphenol 90 to 90% from the viewpoint of improving physical properties. A copolymer of 70% by mass and 2,3,6-trimethylphenol 10-30% by mass is more preferable. Polyphenylene ether (A) may be used individually by 1 type, and may be used together 2 or more types.

  Moreover, the polyphenylene ether (A) may contain other various phenylene ether units as a partial structure as needed. Such a phenylene ether unit is not particularly limited. Specifically, 2- (dialkylaminomethyl) -6-methyl described in JP-A Nos. 01-297428 and 63-301222 is used. Examples include phenylene ether units and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether units.

  The polyphenylene ether (A) may have a small amount of diphenoquinone or the like bonded to the main chain. Furthermore, the polyphenylene ether (A) is partly or entirely selected from the group consisting of acyl functional groups and carboxylic acids, acid anhydrides, acid amides, imides, amines, orthoesters, hydroxy and ammonium carboxylates. It is good also as functionalized polyphenylene ether by making it react (modify | modify) with the functionalizing agent containing 1 type, or 2 or more types.

  The ratio (Mw / Mn value) between the weight average molecular weight Mw and the number average molecular weight Mn of the polyphenylene ether (A) is preferably 2.0 to 5.5, more preferably 2.5 to 4.5, Preferably it is 3.0-4.5. The Mw / Mn value is preferably 2.0 or more from the viewpoint of molding processability of the resin composition, and preferably 5.5 or less from the viewpoint of mechanical properties of the resin composition. The weight average molecular weight Mw and the number average molecular weight Mn are obtained from the polystyrene-equivalent molecular weight by gel permeation chromatography (GPC).

  The reduced viscosity of the polyphenylene ether (A) when measured at 30 ° C. using a chloroform solvent is preferably 0.25 dl / g or more from the viewpoint of sufficient mechanical properties of the resin composition. From the viewpoint of brightness, 0.55 dl / g or less is preferable. More preferably, it is 0.25-0.40 dl / g, More preferably, it is 0.25-0.38 dl / g, More preferably, it is the range of 0.25-0.35 dL / g. In the present embodiment, the reduced viscosity is a value obtained by measuring at 30 ° C. using a chloroform solvent. The reduced viscosity can be controlled by controlling the amount of oxygen or oxygen-containing gas introduced during the polymerization.

  The residual volatile content of the polyphenylene ether (A) is preferably 0.3% by mass (3000 ppm) or less from the viewpoint of improving the surface appearance of the molded article. More preferably, it is 0.1 mass% (1000 ppm) or less. Here, the polyphenylene ether having a residual volatile content of 0.3% by mass or less is not particularly limited. Specifically, the polyphenylene ether can be suitably produced by adjusting the drying temperature and drying time after polymerization of the polyphenylene ether. As said drying temperature, Preferably 40-200 degreeC is mentioned, More preferably, 80-180 degreeC is mentioned, More preferably, 120-170 degreeC is mentioned. 40 ° C. or higher is desirable from the viewpoint of drying efficiency, and drying at 200 ° C. or lower is desirable from the viewpoint of seizure by melting and prevention of deterioration. The drying time is not particularly limited and can be set to 0.5 to 72 hours. Preferably it is 2-48 hours, More preferably, it is 6-24 hours. When the residual volatile matter of the polyphenylene ether (A) is to be removed in a relatively short time, it is preferable to dry the polyphenylene ether (A) at a high temperature. In such a case, in order to prevent deterioration due to heat, drying in a nitrogen atmosphere or drying with a vacuum dryer is preferable.

  In order to reduce the residual volatile content of the polyphenylene ether (A) by drying after polymerization and to reduce the residual volatile content to 0.3% by mass, the polymerization is not adversely affected and the environment is hardly adversely affected. In addition, it is preferable to perform polymerization in advance using a polymerization solvent having a relatively low boiling point and being easily volatilized. Although it does not specifically limit as such a polymerization solvent, Specifically, toluene is mentioned. More specifically, after polymerizing polyphenylene ether having a reduced viscosity of 0.25 to 0.55 dl / g by a known polymerization method, the resulting polymer is sufficiently dried using a vacuum dryer or the like. By doing so, a polyphenylene ether having a residual volatile content of 0.3% by mass can be produced. In addition, even if it uses things other than the above-mentioned preferable polymerization solvent, the polyphenylene ether whose residual volatile matter is in the said range can be manufactured by fully drying.

<Polycarbonate (B)>
Although it does not specifically limit as a polycarbonate (B), Specifically, an aromatic polycarbonate, an aliphatic polycarbonate, and an aromatic-aliphatic polycarbonate are mentioned. Among these, in this embodiment, an aromatic polycarbonate is preferable. Polycarbonate (B) may be used individually by 1 type, and may be used together 2 or more types.

  Although an aromatic polycarbonate is not specifically limited, Specifically, it is obtained by making bihydric phenol and a carbonate precursor react. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Although it does not specifically limit as dihydric phenol, Specifically, hydroquinone, resorcinol, 4,4'- biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenedi Propylidene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5 -Dibromo-4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-3-methyl) Phenyl) fluorene and the like.

  Among these, a preferable dihydric phenol is bis (4-hydroxyphenyl) alkane. Among them, bisphenol A is more preferable from the viewpoint of impact resistance, and 1 from the viewpoint of heat resistance, thermal stability and chemical resistance of the molded body. , 1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC) is more preferred.

  BPTMC is preferably used after being copolymerized with bisphenol A. When the total amount of dihydric phenol is 100 mol%, the preferred total content of BPTMC and bisphenol A is 90 mol% or more, more preferably 93 mol% or more. More preferably, it is 95 mol% or more.

  Furthermore, a preferable range of the ratio of BPTMC and bisphenol A is a range of BPTMC / bisphenol A = 10/90 to 50/50 (molar ratio) from the viewpoint of heat resistance and fluidity.

  Although it does not specifically limit as a carbonate precursor, For example, a carbonyl halide, carbonate ester, or a haloformate etc. are mentioned, Specifically, the dihaloformate of phosgene, diphenyl carbonate, or a bihydric phenol is mentioned.

  When producing an aromatic polycarbonate by interfacial polymerization using a dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used.

  In addition, the aromatic polycarbonate includes a branched aromatic polycarbonate obtained by copolymerization of a trifunctional or higher polyfunctional aromatic compound, and a polyester carbonate obtained by copolymerization of an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. , A copolymer polycarbonate obtained by copolymerizing a bifunctional alcohol (including an alicyclic group), and a polyester carbonate obtained by copolymerizing the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate may be sufficient.

  In addition, although it does not specifically limit as a polyfunctional aromatic compound more than trifunctional, Specifically, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3, 5-dimethyl-4-hydroxyphenyl) ethane can be used.

  When the aromatic polycarbonate contains a polyfunctional compound that produces a branched aromatic polycarbonate, the proportion is preferably 0.001 to 1 mol%, more preferably 0.005 to 0, based on the total amount of the aromatic polycarbonate. 0.9 mol%, more preferably 0.01 to 0.8 mol%.

In addition, when an aromatic polycarbonate is produced by the melt transesterification method, a branched structure may occur as a side reaction, and the amount of the branched structure is also 0.001 to 1 mol% in the total amount of the aromatic polycarbonate. Is more preferable, more preferably 0.005 to 0.9 mol%, still more preferably 0.01 to 0.8 mol%. The content of the polyfunctional compound and the branched structure amount can be calculated by ¹ H-NMR measurement.

  The aliphatic bifunctional carboxylic acid is preferably an α, ω-dicarboxylic acid. Although it does not specifically limit as aliphatic bifunctional carboxylic acid, Specifically, linear saturation, such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, etc. Aliphatic dicarboxylic acids such as aliphatic dicarboxylic acids and cyclohexanedicarboxylic acids are preferred.

  The bifunctional alcohol is preferably an alicyclic diol and is not particularly limited, and specific examples include cyclohexane dimethanol, cyclohexane diol, and tricyclodecane dimethanol.

  The aromatic polycarbonate is not particularly limited, and specifically, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can be used.

  The aromatic polycarbonate includes two types of aromatic polycarbonates such as the above-described aromatic polycarbonates having different dihydric phenols, aromatic polycarbonates containing a branched component, various polyester carbonates, and polycarbonate-polyorganosiloxane copolymers. A mixture of the above may be used.

  Furthermore, what mixed 1 type (s) or 2 or more types can be used also about various types, such as the aromatic polycarbonate from which a manufacturing method differs below, and the aromatic polycarbonate from which a terminal terminator differs.

  In the polymerization reaction of an aromatic polycarbonate, the reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, and it is preferable to carry out the reaction in the presence of an acid binder and an organic solvent.

  Although it does not specifically limit as an acid binder, Specifically, amine compounds, such as alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, or a pyridine, are used.

  Although it does not specifically limit as an organic solvent, Specifically, halogenated hydrocarbons, such as a methylene chloride and chlorobenzene, are used.

  In order to accelerate the reaction, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound may be used. it can.

  When the polymerization reaction of the aromatic polycarbonate is performed by the interfacial polycondensation method, the reaction temperature is preferably 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is 9 or more. Is preferably maintained. In the polymerization reaction by the interfacial polycondensation method, it is preferable to use a terminal terminator. Although it does not specifically limit as a terminal terminator, Specifically, monofunctional phenols can be used. Although it does not specifically limit as monofunctional phenols, Specifically, it is preferable to use monofunctional phenols, such as a phenol, p-tert- butylphenol, and p-cumylphenol. Other examples of monofunctional phenols include decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol, octadecyl phenol, eicosyl phenol, docosyl phenol and triacontyl phenol. Moreover, a terminal terminator may be used independently and may be used in mixture of 2 or more types.

  The reaction by the melt transesterification method in the polymerization reaction of an aromatic polycarbonate is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the dihydric phenol and the carbonate ester are heated in the presence of an inert gas. It is preferably carried out by a method in which the resulting alcohol or phenol is distilled while mixing.

The reaction temperature in the melt transesterification method varies depending on the boiling point of the alcohol or phenol to be produced, but is preferably in the range of 120 to 350 ° C. In the latter stage of the reaction, it is preferable to facilitate the distillation of the alcohol or phenol produced by reducing the pressure of the reaction system to about 1.33 × 10 ^{3 to} 13.3 Pa. The reaction time is preferably about 1 to 4 hours.

  Although it does not specifically limit as carbonate ester, Specifically, ester, such as a C6-C10 aryl group, an aralkyl group, or a C1-C4 alkyl group which may have a substituent, is mentioned. Of these, diphenyl carbonate is preferred.

  A polymerization catalyst can be used to increase the polymerization rate in the melt transesterification method. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt and potassium salt of dihydric phenol; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide; Catalysts such as nitrogen-containing basic compounds such as methylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine can be used. In addition, alkali (earth) metal alkoxides, alkali (earth) metal organic acid salts, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc. The catalyst used for the exchange reaction can be used.

The polymerization catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts to be used is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ^−4, etc. with ^respect to 1 mol of dihydric phenol as a raw material. Selected in a range of quantities.

  In the reaction by the above-described melt transesterification method in the polymerization reaction of an aromatic polycarbonate, in order to reduce phenolic end groups, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenyl, at the end or after the polycondensation reaction. Compounds such as phenyl carbonate and 2-ethoxycarbonylphenyl phenyl carbonate may be added. By reducing the number of phenolic end groups, the stability of the polymer can be improved.

  Furthermore, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Moreover, it is preferable to use the amount of a quencher in the ratio of 0.01-500 ppm with respect to the aromatic polycarbonate after superposition | polymerization, More preferably, it is 0.01-300 ppm, More preferably, it is 0.01-100 ppm. Use as a percentage.

  Preferred deactivators include, for example, phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate, and ammonium salts such as tetraethylammonium dodecyl benzyl sulfate.

  The aromatic polycarbonate preferably has a viscosity average molecular weight of 10,000 or more, more preferably from 15,000 to 50, from the viewpoint of allowing the blended resin composition to exhibit appropriate molding fluidity and mechanical properties. 000. The lower limit of the viscosity average molecular weight is more preferably 16,000, even more preferably 17,000, and still more preferably 18,000. On the other hand, the upper limit of the viscosity average molecular weight is more preferably 26,000, further preferably 25,000, and even more preferably 23,000 from the viewpoint of molding fluidity.

  The aromatic polycarbonate may be a mixture of two or more different aromatic polycarbonates as described above. In this case, it is naturally possible to adjust the viscosity average molecular weight by mixing aromatic polycarbonate having a viscosity average molecular weight outside the preferred range.

  In particular, a mixture with an aromatic polycarbonate having a viscosity average molecular weight exceeding 50,000 has a high entropy elasticity, and has a characteristic that appearance of a molded article due to rheological behavior represented by jetting is less likely to occur. Therefore, when the appearance defect of a molded object arises, it is a suitable aspect to suppress an appearance defect by using a mixture with the aromatic polycarbonate whose viscosity average molecular weight exceeds 50,000. Furthermore, gas injection molding and the like are advantageous because the gas injection amount is stable, and foam molding is advantageous because the foam cells are stable and fine and homogeneous cells are easily formed.

  More preferred is a mixture with an aromatic polycarbonate having a viscosity average molecular weight of 80,000 or more, and further preferred is a mixture with an aromatic polycarbonate having a viscosity average molecular weight of 100,000 or more. That is, an aromatic polycarbonate that can observe a molecular weight distribution of two or more peaks in a measurement method such as gel permeation chromatography (GPC) can be preferably used.

  In the aromatic polycarbonate, the phenolic hydroxyl group content is preferably 30 eq / ton or less, more preferably 25 eq / ton or less, and further preferably 20 eq / ton or less. In addition, the value of the phenolic hydroxyl group amount can be substantially 0 eq / ton by sufficiently reacting the terminal terminator.

The amount of phenolic hydroxyl group is determined by performing ¹ H-NMR measurement, calculating the molar ratio of a divalent phenol unit having a carbonate bond, a divalent phenol unit having a phenolic hydroxyl group, and a terminal terminator unit, and based on this, the polymer weight It is calculated | required by converting into the amount of per phenolic hydroxyl groups.

The viscosity average molecular weight (Mv) of the aromatic polycarbonate can be determined as follows. First, the specific viscosity is calculated by the following mathematical formula (I). In the following formula (I), the drop time (t ₀ ) of methylene chloride and the drop time (t) of the sample solution are obtained by using a solution obtained by dissolving 0.7 g of aromatic polycarbonate at 20 ° C. in 100 ml of methylene chloride. It can be determined by an Ostwald viscometer. The viscosity average molecular weight M can be obtained by inserting the specific viscosity into the following formula (II).
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ ... Formula (I)
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]

The obtained specific viscosity is substituted into the following formula (II) to obtain the intrinsic viscosity [η], and the obtained intrinsic viscosity is substituted into the following formula (III) to obtain the viscosity average molecular weight M.
η _SP /c=[η]+0.45×[η] ² c (where [η] is intrinsic viscosity, c = 0.7)... Formula (II)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83 ... Formula (III)

  As described above, aromatic polycarbonates are different in dihydric phenol, those using and not using a terminator, linear ones and branched ones, those having different production methods, and terminal terminations. Two or more kinds of aromatic polycarbonates such as those having different agents, aromatic polycarbonates and polyester carbonates, and those having different viscosity average molecular weights can be mixed and used.

  The polycarbonate (B) used in the present embodiment is preferably an aromatic polycarbonate resin produced by a melt transesterification method (non-phosgene method) from the viewpoint of moldability of the molded body and appearance (white spots) improvement. Furthermore, the polycarbonate (B) is more preferably a polyester carbonate resin having a molecular skeleton copolymerized with isophthalic acid and / or terephthalic acid from the viewpoint of heat resistance, thermal stability and chemical resistance of the molded product.

  The aliphatic polycarbonate is not particularly limited. In addition, the aromatic-aliphatic polycarbonate is not particularly limited, and specific examples thereof include a copolymer of the aromatic polycarbonate and the aliphatic polycarbonate.

  The melt flow rate (MFR) of the polycarbonate (B) is preferably selected from the range of 1 to 100, more preferably 5 to 65, still more preferably 8 to 40, and even more preferably 8 to 30. The MFR is preferably 1 or more from the viewpoint of imparting sufficient fluidity, and is preferably 100 or less from the viewpoint of sufficient miscibility with the polyphenylene ether resin and suppression of hydrolysis during extrusion molding. The MFR is a value measured at a measurement temperature of 300 ° C. and a load of 1.2 kg in accordance with the test method ISO1133.

  When the polycarbonate (B) is a polycarbonate resin composed of 95 mol% or more of bisphenol A as a dihydric phenol, from the viewpoint of forming a polycarbonate as a dispersed phase using a polyphenylene ether as a matrix, the measurement temperature is 300 ° C. The MFR value measured with a 1.2 kg load is preferably in the range of 10 to 50 g / 10 min. More preferably, it is 10-30 g / 10min.

  In the case where the polycarbonate (B) is a polycarbonate resin containing 90 mol% or more of bisphenol A and bisphenol TMC (BPTMC) monomers as dihydric phenols, ISO 1133 is formed from the viewpoint of forming polycarbonate as a dispersed phase using polyphenylene ether as a matrix. The MFR value measured at a measurement temperature of 330 ° C. and a load of 2.16 kg is preferably in the range of 10 to 50 g / 10 min. More preferably, it is 10-30 g / 10min.

  The water content of the polycarbonate (B) is preferably 1500 ppm or less. More preferably, it is 500 ppm or less, More preferably, it is 300 ppm or less, More preferably, it is 200 ppm or less. From the viewpoint of strand take-out stability at the time of extrusion and suppression of generation of silver on the surface of the molded product due to hydrolysis at the time of molding, the content is preferably 1500 ppm or less. The water content can be measured with a Karl Fischer moisture meter or the like.

  Moreover, the polycarbonate (B) used for this embodiment may contain the polycarbonate oligomer in order to aim at the improvement of a molded object external appearance, and the improvement of fluidity | liquidity. The polycarbonate oligomer has a viscosity average molecular weight (Mv) of preferably 1,500 to 9,500, more preferably 2,000 to 9,000. The method for measuring the viscosity average molecular weight (Mv) is the same as the method for measuring the viscosity average molecular weight of the aromatic polycarbonate. The content of the polycarbonate oligomer is preferably 30% by mass or less in the polycarbonate (B).

  Furthermore, in this embodiment, as the polycarbonate (B), not only a virgin resin but also a polycarbonate resin regenerated from a used product, a so-called material-recycled polycarbonate resin may be used. Used products include, for example, optical recording media such as optical disks, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields, and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, etc.・ Construction materials such as corrugated sheet. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The use ratio of the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, based on the virgin resin.

  The resin composition of this embodiment contains polycarbonate (B) from the viewpoint of eliminating white spots on the surface of the molded product, in addition to heat resistance and molding processability. Content of a polycarbonate (B) is 5-45 mass parts with respect to 100 mass parts of polyphenylene ether (A). Preferably it is 10-40 mass parts, More preferably, it is 15-30 mass parts.

  Even if polystyrene is added to polyphenylene ether (A), the amount of vitiligo is hardly changed, but 5% by mass or more of polycarbonate (B) in 100% by mass of polyphenylene ether (A) and polycarbonate (B) in total. By using it, the occurrence of vitiligo is dramatically suppressed. As the amount of polycarbonate (B) added increases, the occurrence of vitiligo can be suppressed. However, the amount of polycarbonate (B) added should be 31% by mass or less in the total of 100% by mass of polyphenylene ether (A) and polycarbonate (B). For example, polyphenylene ether and polycarbonate are kneaded well, and die swell during extrusion is less likely to occur, which facilitates continuous production. From the above viewpoint, the polyphenylene ether / polycarbonate resin of the present embodiment preferably contains 70 to 95% by mass of polyphenylene ether (A) and 5 to 30% by mass of polycarbonate (B), and polyphenylene ether (A) 75. It is more preferable to contain -90 mass% and polycarbonate (B) 10-25 mass%.

<Phosphate ester flame retardant (C)>
The phosphate ester flame retardant (C) has a great effect on imparting flame retardancy to the polyphenylene ether / polycarbonate resin composition. Although it does not specifically limit as a phosphate ester type flame retardant which can be used as (C) component, Specifically, a phosphate ester compound, a phosphazene compound, etc. are mentioned.

  The phosphate ester compound is added to improve flame retardancy, and any organic phosphate ester generally used as a flame retardant can be used. Specific examples of the phosphate compound include triphenyl phosphate, trisnonylphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis [di (2,6-dimethylphenyl) phosphate], 2,2-bis {4- [ Examples thereof include, but are not limited to, bis (phenoxy) phosphoryloxy] phenyl} propane, 2,2-bis {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane, and the like. In addition to the above, the phosphate ester compound is not particularly limited, but for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, Phosphate ester compounds such as diisopropylphenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphonate, diphenyl-4 -Hydroxy-3,5-dibromobenzyl phosphonate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) Phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, bis (chloropropyl) monooctyl phosphate hydroquinonyl diphenyl phosphate, phenylnonylphenyl hydroxide Examples thereof include monophosphate compounds such as nonyl phosphate and phenyl dinonylphenyl phosphate, and aromatic condensed phosphate compounds described later. The phosphate ester flame retardant (C) may be used alone or in combination of two or more.

  Among these, aromatic condensed phosphate ester compounds are preferably used because they generate less gas during processing and are excellent in thermal stability.

  These aromatic condensed phosphate ester compounds are generally commercially available. For example, CR741, CR733S, PX200 manufactured by Daihachi Chemical Industry Co., Ltd., FP600, FP700, FP800 manufactured by ADEKA Co., Ltd., and the like are known.

The phosphate ester flame retardant (C) used in the present embodiment is preferably a phosphate ester compound (aromatic condensed phosphate ester compound) represented by the following formula (I) or the following formula (II). is there. More preferred is a phosphate ester compound (aromatic condensed phosphate ester compound) represented by the following formula (I).
(In formulas (I) and (II), Q1, Q2, Q3, and Q4 are each a substituent and each independently represents an alkyl group having 1 to 6 carbon atoms, and R1 and R2 each represents a methyl group. , R3 and R4 each independently represents a hydrogen atom or a methyl group, n is an integer of 1 or more, n1 and n2 each independently represents an integer of 0 to 2, and m1, m2, m3 and m4 are each Independently represents an integer of 0 to 3.)

  In the aromatic condensed phosphate compound represented by the above formulas (I) and (II), n is an integer of 1 or more, preferably an integer of 1 to 3, in each molecule.

  Among the aromatic condensed phosphate compounds represented by the above formulas (I) and (II), preferred aromatic condensed phosphate compounds are those in which m1, m2, m3, m4, n1, and n2 in the formula (I) are 0. An aromatic condensed phosphate ester compound in which R3 and R4 are methyl groups; or Q1, Q2, Q3, Q4, R3, and R4 in formula (I) are methyl groups, and n1 and n2 are 0 And m1, m2, m3, and m4 are integers of 1 to 3, and the range of n is an integer of 1 to 3, in particular, n is an aromatic condensed phosphate ester compound. In particular, a phosphate ester flame retardant (C) containing 50% by mass or more of the preferable phosphate ester compound is preferable.

  More preferable among these aromatic condensed phosphate compounds are aromatic condensed phosphate compounds having an acid value of 0.1 or less (value obtained in accordance with JIS K2501).

  Moreover, as a phosphazene compound, a phenoxy phosphazene and its crosslinked body are preferable, and the phenoxy phosphazene compound whose acid value is 0.1 or less (value obtained based on JIS K2501) is more preferable.

  (C) The compounding quantity of a component is 3-10 mass parts with respect to a total of 100 mass parts of (A) and (B) component from a viewpoint of a flame retardance, heat resistance, and a mechanical physical property, and 3-9 A mass part is preferable and 4-8 mass parts is more preferable. Phosphoric ester-based flame retardants greatly reduce the heat resistance of the flame-retardant resin composition and the appearance of molded products such as vitiligo with the increase in the amount used, so the minimum necessary to obtain the desired flame retardancy Select the limit usage. From this viewpoint, the amount of 3 to 10 parts by mass is preferable because the appearance of the molded product such as white spots is improved.

<A flame retardant (D) which is a polystyrene and/or acrylonitrile-styrene copolymer into which a sulfonic acid group and/or a sulfonic acid group is introduced>
The polystyrene or acrylonitrile-styrene copolymer (AS resin) used in the flame retardant (D) is not particularly limited, but specifically, polystyrene, high impact polystyrene, (HIPS: styrene-butadiene copolymer), Acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylate copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene resin (AES resin), An acrylonitrile-ethylene-propylene-diene-styrene resin (AEPDMS resin) etc. can be mentioned, Among these, any 1 type or multiple types can be mixed and used.

  The weight average molecular weight of these resins is preferably in the range of 25,000 to 10,000,000, more preferably 30,000 to 1 from the viewpoint of exhibiting sufficient flame retardancy for use as a reflector or extension of a lamp. In the range of 50,000,000, more preferably in the range of 50,000 to 500,000. In addition, a weight average molecular weight is obtained from a polystyrene conversion molecular weight by gel permeation chromatography (GPC).

  As a method for introducing a sulfonic acid group and / or a sulfonic acid group into the above-described resin, there is a method of sulfonating with a predetermined amount of a sulfonating agent. The sulfonating agent is not particularly limited, and specific examples include sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, and polyalkylbenzenesulfonic acids, and any one or more of these may be mixed. Can be used. As another example of the sulfonating agent, a complex with a Lewis base such as an alkyl phosphate ester or dioxane can be used.

  The water content of the sulfonating agent is preferably less than 3% by mass from the viewpoint of preventing discoloration of the resin and reduction in mechanical strength due to by-products of amide groups and carboxyl groups.

Examples of the state of the introduced sulfonating agent include a state of a sulfonic acid group (—SO ₃ H), a state of a sulfonate group, and a state neutralized with ammonia or an amine compound. Although it does not specifically limit as a sulfonate group, Specifically, sulfonate Na base, sulfonate K base, sulfonate Li base, sulfonate Ca base, sulfonate Mg base, sulfonate Al base, sulfonate Zn base And sulfonic acid Sb base and sulfonic acid Sn base.

  In addition, from the viewpoint of imparting higher flame retardancy, polystyrene or AS resin into which a sulfonate group is introduced rather than a sulfonate group is preferable. Among the sulfonic acid bases, sulfonic acid Na base, sulfonic acid K base, sulfonic acid Ca base and the like are preferable.

  The introduction rate of the sulfonic acid group and / or sulfonic acid base can be adjusted by the addition amount of the sulfonating agent, the reaction time of the sulfonating agent, the reaction temperature, the type and amount of the Lewis base, and the like. Among these methods, it is more preferable to adjust the addition amount of the sulfonating agent, the reaction time with the sulfonating agent, the reaction temperature and the like.

  From the viewpoint of sufficiently imparting flame retardancy, the introduction ratio of sulfonic acid groups and / or sulfonic acid groups to polystyrene and / or AS resin is preferably 0.001% by mass or more, more preferably 0.01% as a sulfur component. It is at least mass%, more preferably at least 0.1 mass%. The introduction rate of the sulfonic acid group and / or sulfonic acid group is preferably 20% by mass or less from the viewpoint of making the flame-retardant resin composition less susceptible to change with time (water absorption) and preventing the blooming time during combustion from becoming long. 10 mass% or less is more preferable, and 5 mass% or less is further more preferable. The sulfur component in the flame retardant can be quantified by an oxygen flask combustion method. If the sulfur component is quantified according to JIS K 6233-1, the introduction rate of sulfonic acid groups and / or sulfonic acid groups can be determined by calculation.

  The flame retardant resin composition of the present embodiment contains 0.05 to 1.0 part by mass of the flame retardant (D), preferably 0.05 to 0.8 part by mass, It is more preferable to include parts by mass. This flame retardant has the feature of exhibiting an effect with a very small amount of use, and even if it is added in excess of the above content, no significant problem will occur, but the above content is sufficient.

<Styrene resin (E) not reinforced with rubber>
In the flame-retardant resin composition of the present embodiment, 0-30 parts by mass of the styrene-based resin (E) that is not reinforced with rubber is 100 parts by mass with respect to a total of 100 parts by mass of the component (A) to the component (D). Further can be included. From the viewpoint of improving the brightness of the molded body and improving the melt fluidity during molding, the content of the component (E) is preferably 0 to 30 parts by mass, and 3 to 25 parts by mass. Is more preferably 5 to 20 parts by mass.

By containing the styrene resin (E) which is not reinforced with rubber, it is possible to improve the feeling of brightness of the molded body and improve the melt fluidity during molding. One of the merits of selecting a styrene resin (E) that is not rubber-reinforced as a melt fluidity improver is that the heat resistance of the flame retardant resin composition of the present embodiment is hardly impaired even when added. It can also be mentioned. The styrene resin (E) not reinforced with rubber is obtained by polymerizing a styrene compound alone or a styrene compound and a compound copolymerizable with the styrene compound in the absence of a rubbery polymer. It is a synthetic resin obtained. Although a styrene-type compound is not specifically limited, Specifically, it means the compound represented by following formula (3).

  In the formula (3), R is hydrogen, lower alkyl or halogen, Z is one or more selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is 0-5. Is an integer. Although it does not specifically limit as a styrene-type compound represented by Formula (3), Specifically, styrene, (alpha) -methylstyrene, 2, 4- dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert- Examples include butyl styrene and ethyl styrene. In addition, the compound copolymerizable with the styrene compound is not particularly limited, and specifically, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; maleic anhydride And the like, and used together with a styrenic compound.

  Among these, the styrene-based resin (E) not reinforced with rubber is one kind selected from acrylonitrile-styrene (AS) resin having an acrylonitrile (AN) unit content of 5 to 15% by mass, and general-purpose polystyrene composed of styrene units. Two or more styrenic resins are preferred. The content of the acrylonitrile unit in the acrylonitrile-styrene resin is preferably 5 to 15% by mass from the viewpoint of improving the surface appearance of the obtained molded product and ensuring sufficient miscibility with the polyphenylene ether. Preferably it is 5-12 mass%, More preferably, it is 7-10 mass%.

  When the component (E) is an acrylonitrile-styrene (AS) resin having an acrylonitrile (AN) unit content of 5 to 15% by mass, a polyphenylene ether is used as a matrix to form a dispersed phase of the polycarbonate (B). It is possible to finely disperse the polycarbonate up to a range where the polycarbonate content is higher.

<Styrenic block copolymer (F)>
In the flame retardant resin composition of the present embodiment, the styrenic block copolymer (F) is added in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass in total of the component (A) to the component (D). Furthermore, it is preferable to include. The content of the styrenic block copolymer (F) is more preferably 1 to 10 parts by mass, and further preferably 2 to 10 parts by mass. If the content is in such a range, the impact resistance is higher. Moreover, if content is 10 mass parts or less, it is excellent in the surface external appearance of a molded object, and if it is 0.5 mass part or more, there exists a tendency for impact resistance to become high.

  Although it does not specifically limit as a styrene-type block copolymer (F), Specifically, the block copolymer (henceforth a "styrene block-conjugated diene compound block copolymer") which has a styrene block and a conjugated diene compound block. It is also referred to as a hydrogenated product. The conjugated diene compound block is preferably hydrogenated at a hydrogenation rate of 50% or more from the viewpoint of thermal stability. More preferably, it is 80% or more, More preferably, it is 95% or more.

  The PPE / PC flame retardant resin composition containing the styrene block copolymer (F) tends to have high impact resistance. The styrenic block copolymer (F) may be used alone or in combination of two or more.

  The conjugated diene compound block is not particularly limited, and specific examples include polybutadiene, polyisoprene, poly (ethylene butylene), poly (ethylene propylene), and vinyl-polyisoprene. A conjugated diene compound block may be used individually by 1 type, and may be used in combination of 2 or more type.

  The arrangement of the repeating units constituting the block copolymer may be a linear type or a radial type. Further, the block structure constituted by the polystyrene block and the rubber intermediate block may be any of two types, three types, and four types. Among these, from the viewpoint that the desired effect can be sufficiently exhibited in the present embodiment, a three-type linear type block copolymer composed of a polystyrene-poly (ethylene / butylene) -polystyrene structure is preferable. The conjugated diene compound block may contain butadiene units within a range not exceeding 30% by mass.

  In the resin composition of the present embodiment, a styrene block copolymer into which a functional group such as a carbonyl group or an amino group is introduced can be used as the styrene block copolymer (F).

  The carbonyl group is introduced by modification with an unsaturated carboxylic acid or a functional derivative thereof. Examples of the unsaturated carboxylic acid or functional derivative thereof are not particularly limited, and specifically include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid. And dicarboxylic acids such as endo-cis-bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid, and anhydrides, ester compounds, amide compounds and imide compounds of these dicarboxylic acids; acrylic acid and Examples thereof include monocarboxylic acids such as methacrylic acid, and ester compounds and amide compounds of these monocarboxylic acids. Among these, maleic anhydride is preferred from the viewpoint of maintaining the surface appearance of the molded body and imparting impact resistance. The amino group is not particularly limited, but specifically, it is introduced by reacting an imidazolidinone compound, a pyrrolidone compound, or the like with a styrene block copolymer.

  The component (F) contains a hydrogenated styrene-conjugated diene compound block copolymer having a bound styrene content of 45 to 80% by mass from the viewpoint of improving the gloss of the molded product and preventing delamination of the molded product. preferable.

  In the resin composition used in the present embodiment, a styrene-conjugated diene compound block having a bound styrene content of 45 to 80% by mass from the viewpoint of improving the gloss of the molded product, imparting a further impact resistance, and preventing delamination of the molded product. A hydrogenated product (F-1) of a copolymer and a hydrogenated product (F-2) of a styrene-conjugated diene compound block copolymer having a bound styrene content of 20 to 40% by mass, (F-1) It is preferable to use a combination of / (F-2) = 4/1 to 1/4. More preferably, (F-1) / (F-2) = 3/2 to 1/3, and still more preferably a ratio of 1/1 to 1/2. From the viewpoint of imparting sufficient impact resistance, the component (F-2) is preferably blended at a ratio of (F-1) / (F-2) = 4/1 or less. In addition, from the viewpoint of sufficient improvement of the gloss of the molded product and prevention of delamination, the component (F-2) may be blended at a ratio of (F-1) / (F-2) = 1/4 or more. preferable.

  The amount of bound styrene of the component (F-1) is selected from the range of 45 to 80% by mass, preferably 50 to 75% by mass, and more preferably 55 to 70% by mass. The amount of bound styrene of the component (F-1) is preferably 45% by mass or more from the viewpoint of suppressing delamination by mixing with the component (F-2), and preferably 80% by mass or less from the viewpoint of maintaining impact resistance.

  The amount of bound styrene of the component (F-2) is selected from the range of 20 to 40% by mass, preferably 25 to 40% by mass, and more preferably 25 to 35% by mass. The amount of bound styrene of the component (F-2) is preferably 20% by mass or more from the viewpoint of miscibility with the component (A), and preferably 40% by mass or less from the viewpoint of imparting sufficient impact resistance.

  The number average molecular weight of the component (F-1) is preferably 5,000 to 150,000, more preferably 10,000 to 120,000, and still more preferably 30,000 to 100,000. From the viewpoint of miscibility with the polyphenylene ether (A), a range of 5,000 to 150,000 is preferable.

  The number average molecular weight of the component (F-2) is preferably 50,000 to 500,000, more preferably 100,000 to 400,000, and still more preferably 150,000 to 300,000. From the viewpoint of imparting sufficient impact resistance, a range of 50,000 to 500,000 is preferable.

  The ratio (Mw / Mn value) of the weight average molecular weight Mw and the number average molecular weight Mn of the component (F) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, and still more preferably. It is in the range of 1.0 to 1.5. From the viewpoint of mechanical properties, a range of 1.0 to 3.0 is preferable. The weight average molecular weight Mw and the number average molecular weight Mn are obtained from the polystyrene-equivalent molecular weight.

<Others>
The resin composition of the present embodiment preferably does not contain an inorganic filler as a reinforcing agent from the viewpoint of maintaining the brightness of the molded body. Although it does not specifically limit as an inorganic filler as a reinforcing agent, Specifically, it is used for reinforcement of a thermoplastic resin, For example, glass fiber, carbon fiber, glass flakes, talc, and mica are mentioned.

  The resin composition of the present embodiment preferably does not contain a crystalline polymer from the viewpoint of maintaining the brightness of the molded body. The crystalline polymer is not particularly limited, and specific examples include polyamide, polypropylene, polyethylene, polyphenylene sulfide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, and liquid crystal polymer.

  In addition, the resin composition of the present embodiment may contain inorganic and organic colorants, release agents, and the like as necessary.

  A stabilizer may be used from the viewpoint of improving the thermal stability of the resin composition and the surface appearance and brightness of the molded product. The stabilizer is not particularly limited, and specific examples include hindered phenol-based, phosphorus-based heat stabilizers, hydroxylamine-based, vitamin E-based heat stabilizers, and the like. Also included are compounds such as cyanoacrylate-based, benzophenone-based, and cinnamic acid ester-based compounds that are usually used as ultraviolet absorbers.

≪Method for producing resin composition≫
The flame retardant resin composition of this embodiment can be produced by melt-kneading each component. The conditions for melt kneading for producing the flame retardant resin composition are not particularly limited, but a large amount of resin composition that is excellent in surface appearance and can sufficiently exhibit heat resistance and flame retardant performance. From the viewpoint of obtaining it stably, it is preferable to use a twin screw extruder. As an example, ZSK25 twin screw extruder (manufactured by German company Werner & Pfleiderer, barrel number 10, screw diameter 25 mm, L / D = 44); kneading disc L: 2, kneading disc R: 6, and kneading disc N: a screw pattern having two), a method of melt kneading under conditions of a cylinder temperature of 270 to 340 ° C., a screw rotation speed of 150 to 450 rpm, and a vent vacuum degree of 11.0 to 1.0 kPa can be mentioned. . L represents the distance (m) from the raw material supply port to the discharge port of the twin screw extruder, and D represents the screw diameter (m) of the twin screw extruder.

  When producing a flame retardant resin composition using a larger-sized (screw diameter of 40 to 90 mm) twin screw extruder, attention should be paid to the component (A) generated during extrusion into the extruded resin pellet. This is a mixture of gels and carbides, which may cause a reduction in the surface appearance and brightness of the molded body. Therefore, it is preferable that the component (A) is introduced from the most upstream (top feed) raw material inlet and the oxygen concentration inside the shooter at the uppermost inlet is set to 3% by volume or less. The oxygen concentration is more preferably 1% by volume or less.

  To adjust the oxygen concentration, the inside of the raw material storage hopper is sufficiently replaced with nitrogen, and a tape is put in the middle of the feed line from the raw material storage hopper to the raw material inlet of the extruder to prevent air from entering and exiting. This can be achieved by adjusting the nitrogen feed amount and adjusting the opening of the vent hole after improving the sealing performance. From the viewpoint of reducing gel and carbide generation during extrusion, the oxygen concentration inside the shooter is preferably 3% by volume or less.

≪Molded body, automotive lamp extension parts, extension parts of various lighting fixtures, reflector parts of various lighting fixtures, and manufacturing methods thereof≫
A molded body, an automotive lamp extension component, an extension component of various lighting fixtures, and a reflector component including the flame retardant resin composition of the present embodiment can be obtained by molding the above-mentioned flame retardant resin composition.

  There are no particular restrictions on the molding method used to produce molded articles, automotive lamp extension parts, or various lighting fixture extensions and reflector parts using the PPE / PC flame retardant resin composition. For example, injection molding, extrusion Preferred examples include molding, vacuum molding and pressure molding, and injection molding is more preferably used from the viewpoint of molding appearance and brightness.

  The automobile lamp extension component refers to a relatively large light reflecting component that exists between a reflector, which is a light reflecting component behind a light source beam of an automobile headlamp, and a lamp front cover. Automotive lamp extension parts do not require heat resistance as high as that of reflectors, but they have good brightness on the glossy surface of the molded product, surface appearance after aluminum deposition, sufficient balance between heat resistance and molding fluidity, and light weight Property (being a low specific gravity material), flame retardancy, etc. are required at a higher level.

  The extension part and reflector part of a lighting fixture mean the reflective material and reflection design member of various lighting fixtures, such as household appliances, industrial, and agriculture. As with automotive lamp extension parts, it is required to have good brightness on the glossy surface of the molded product, surface appearance after vapor deposition of aluminum, light weight, and excellent flame retardancy. The required heat resistance is not as high as that of automotive lamp extension parts, but some parts are larger than automotive lamp extension parts, so it is made of a flame-retardant resin composition having high molding fluidity. Is preferred.

  The molding temperature of the automotive lamp extension component of this embodiment or the extension component or reflector component of various lighting fixtures is selected from the range of 270 to 340 ° C., for example, a cylinder set temperature (maximum temperature part). 280-330 degreeC is preferable, 290-320 degreeC is more preferable, 300-320 degreeC is further more preferable. 270 ° C. or higher is preferable from the viewpoint of sufficient molding fluidity, and 340 ° C. or lower is preferable from the viewpoint of thermal stability of the resin composition.

  It is preferable that the average thickness of the automotive lamp extension component of this embodiment or the extension component or reflector component of various lighting fixtures is selected from the range of 0.8 to 3.2 mm. The average thickness is more preferably 1.0 to 3.0 mm, further preferably 1.2 to 2.5 mm, and still more preferably 1.4 to 2.2 mm. The average thickness is preferably 3.2 mm or less from the viewpoint of lightness, and is preferably 0.8 mm or more from the viewpoint of sufficient moldability and strength retention.

  For automotive lamp extension parts or extension parts and reflector parts of various lighting fixtures, mirror surface molds polished with diamond paste etc. to a very small level (average surface roughness of 0.2 μm or less) are used. It is preferable to be molded using. The polishing count of the mirror mold is preferably # 1000 or more, more preferably # 2000 or more, and further preferably # 5000 or more. From the viewpoint of sufficient mirror appearance, the polishing count is preferably # 1000 or more.

  The automotive lamp extension component or the extension component or reflector component of various lighting fixtures is preferably subjected to aluminum vapor deposition treatment on a part or all of the surface of the molded product after molding. Since the automotive lamp extension part of this embodiment or the extension parts and reflector parts of various lighting fixtures can improve the adhesion of the aluminum film by activating the surface of the molded body before aluminum deposition, plasma treatment is performed in advance. Is preferably performed. In addition, it is preferable to coat the silicon dioxide polymer film on the surface of the molded body after aluminum deposition by plasma polymerization in order to prevent the appearance and brightness from being lowered due to oxidation or the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not restrict | limited only to these Examples. The measurement methods and raw materials of physical properties used in Examples and Comparative Examples are shown below.

[Measurement method of physical properties]
The test pieces used for measuring the physical properties were all formed pieces produced as follows. The resin composition pellets obtained in Examples and Comparative Examples were dried in a hot air dryer at 120 ° C. for 3 hours. The dried resin composition pellets were molded by an injection molding machine (IS-80EPN, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 300 ° C., a mold temperature of 120 ° C., and an injection speed (panel set value) of 85%, and the thickness was 0 A shaped piece of .64 cm tanzania shape was obtained. Moreover, about what was required for the test to implement, the 0.32 cm-thick dumbbell-shaped molded piece and the 0.16 cm tanza-shaped molded piece were obtained.

In each sample, a 0.32 cm-thick dumbbell molded piece was molded with a molded piece SSP (short shot pressure) +5 kg / cm ² gauge pressure, molding cycle: injection time / cooling time = 10 sec / 10 sec, and thickness 0 The .64 cm Tanzaku molded piece was molded at the same SSP gauge pressure as the dumbbell molded piece, with a molding cycle: injection time / cooling time = 15 sec / 15 sec. SSP + 5 kg / cm ² gauge pressure, molding cycle: injection time / cooling time = 10 sec / 10 sec.

1. Deflection temperature under load (HDT)
According to ASTM D648, using a resin composition obtained in the following examples and comparative examples, a 0.64 cm-thick tanzania molded piece produced by the above molding method was used and measured at a load of 1.8 MPa.
Automotive lamp extension parts or extensions and reflector parts of various lighting fixtures require an HDT of at least 120 ° C.

2. Fluidity (MFR)
The pellets of the resin composition obtained in Examples 6 and 10 to 12 were dried in a hot air dryer at 120 ° C. for 3 hours. For the resin compositions obtained in Examples 7 to 11 at a cylinder set temperature of 250 ° C. and a load of 10 kg using a melt indexer (P-111, manufactured by Toyo Seiki Co., Ltd.) after drying, the cylinder set temperature is 280. MFR (melt flow rate) was measured at 10 ° C. under a load of 10 ° C.
As an evaluation standard, it was determined that the higher the MFR, the more advantageous the material design in this application.

3. IZOD impact value Measured at 23 ° C. according to ASTM D256, using the resin composition obtained in Examples 6 and 10 to 12 and using a 0.64 cm thick tanzania molded piece produced by the above molding method. did.
As an evaluation standard, it was determined that the higher the IZOD impact value, the more advantageous in terms of material design for this application.

4). Gloss value (Gloss: Measurement angle 20 °)
Using the resin compositions obtained in Examples 6 and 10-12, the central part of a dumbbell molded piece having a thickness of 0.32 cm produced by the above molding method was used as a gloss meter (VG7000, manufactured by Nippon Denshoku Industries Co., Ltd.). Thus, the gloss value (gloss) at a measurement angle of 20 ° was measured.
As an evaluation standard, the higher the gloss value, the higher the gloss of the molded piece and the better the brightness.

5. Number of vitiligo (craters having a diameter of 30 μm or more) The pellets of the resin composition obtained in the following examples and comparative examples were dried in a hot air dryer at 120 ° C. for 3 hours. The resin composition after drying was subjected to cylinder injection by an injection molding machine (IS-80EPN, manufactured by Toshiba Machine Co., Ltd.) equipped with a film gate mirror mold having a size of 100 mm × 100 mm × 2 mm with the mold surface polished to # 5000. A molded flat plate was obtained by molding at a temperature of 320 ° C., a mold temperature of 100 ° C., an injection pressure (gauge pressure of 70 MPa), and an injection speed (panel set value) of 85%. Furthermore, the obtained shaped flat plate is placed in a vacuum deposition apparatus, an inert gas and oxygen are introduced into the device, the inside of the chamber is brought into a plasma state, and plasma treatment is performed to activate the shaped flat plate surface. Then, aluminum was deposited on the formed flat plate in a vacuum deposition apparatus. Furthermore, as a protective film for the aluminum deposition surface, plasma polymerization treatment was performed to form a silicon dioxide polymer film. The aluminum film thickness was 80 nm and the silicon dioxide film thickness was 50 nm. A 40 × magnified photograph was taken with a digital microscope (model: VHX1000, manufactured by Keyence Corporation) at the center of the aluminum vapor deposition surface of the formed flat plate (hereinafter also referred to as “aluminum vapor deposition flat plate”) on which this aluminum vapor deposition was performed. The total of the number of projections having crater-like depressions with a diameter of 30 μm or more existing in one field of view (area: 52.4 mm ² ) (the traces of gas escape during molding) for all five mirror-molded flat plates Was divided by 5 to calculate the average number per field of view. The average number was defined as the number of vitiligo.
The evaluation was evaluated by ○ to × as follows according to the average number per field of view.
○: 0 to 15 per visual field △: 16 to 25 per visual field ×: 26 or more per visual field

6). Appearance of aluminum deposition surface of molded flat plate (visual)
Using the resin compositions obtained in the examples and comparative examples, the aluminum vapor deposition surface of the aluminum vapor deposition flat plate produced by the above method was visually observed and evaluated according to the following ranks. It was determined that those with ○ or Δ can be used more suitably in lamp component applications.
○: No defects such as white spots, silver streaks, or cloudiness are observed visually. Δ: Slight defects are observed. ×: Many defects are observed and the appearance is clearly defective.

7). Flame retardancy UL-94 5th Ed. Thus, a VB test was performed using a molded piece having a thickness of 1.6 mm.
The number of combustion seconds after the first flame contact and the second flame contact of the five molded pieces (thickness 0.16 cm) was measured, and ranking was performed according to the combustion time by the flame contact of 10 times in total. The smaller the rank, the better the flame retardancy.
V-0: Total combustion time ≦ 50 seconds, maximum number of combustion seconds per time ≦ 10 seconds, no cotton ignition due to dripping during combustion.
V-1: Total combustion time ≦ 250 seconds, maximum combustion time per time ≦ 30 seconds, no cotton ignition due to dripping during combustion.
V-2: Total combustion time ≦ 250 seconds, maximum combustion time per time ≦ 30 seconds, cotton ignition due to dripping during combustion.

8). Extrusion mass productivity As an index of stability during melt-kneading by an extruder, the presence or absence of die swell in the resin strand flowing out from the die head was evaluated.
○: No die swell. (Good mass productivity)
Δ: accompanied by mild die swell. (Extrudable but requires some allowance for mass productivity)
X: A thing with a large die swell. (Cannot be mass-produced, causing strand breaks in seconds to minutes)

[raw materials]
<Polyphenylene ether (A)>
(A-1) Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.50 dl / g poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter also referred to as “A-1”) Used). The residual volatile content of A-1 was 0.24% (2400 ppm). In addition, A-1 was dried for 3 hours in the vacuum volatilization furnace set to 180 degreeC, and the weight difference of A-1 before and behind drying was calculated | required as a residual volatile matter.

  (A-2) Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.30 dl / g poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter also referred to as “A-2”) Used). The residual volatile content of A-2 was 0.28% (2800 ppm). In addition, A-2 was dried for 3 hours in the vacuum volatilization furnace set to 180 degreeC, and the weight difference of A-2 before and behind drying was calculated | required as a residual volatile matter.

<Polycarbonate (B)>
(B-1) MFR (Test conditions: ISO 1133, measured at 300 ° C. under a 1.2 kg load) 10 g / 10 min polycarbonate resin produced by the melt transesterification method (Wonderlite PC-110 [registered trademark], Asahi Kasei Co., Ltd.) Manufactured, hereinafter referred to as “B-1”).

<Phosphate ester flame retardant (C)>
(C-1) Aromatic condensed phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.)

<A flame retardant (D) which is a polystyrene and/or acrylonitrile-styrene copolymer into which a sulfonic acid group and/or a sulfonic acid group is introduced>
(D-1) 3 g of general purpose polystyrene having a weight average molecular weight of 200,000 measured by GPC as polystyrene is put into a round bottom flask into which 27 g of 1,2-dichloroethane has been injected, and heated to 50 ° C. to dissolve. It was. Subsequently, 3.5 g of anhydrous sulfuric acid was added, and the mixture was stirred for 1 hour at room temperature to carry out sulfonation treatment. Next, air was bubbled into the flask to remove the remaining sulfuric acid gas. The reaction solution was poured into boiling pure water to remove the solvent, and after the temperature was lowered to room temperature, the pH was adjusted to 7 with potassium hydroxide. Subsequently, it filtered with the glass filter and also wash | cleaned 3 times with pure water. The obtained solid was dried under reduced pressure at 60 ° C. to obtain a dried solid (a flame retardant in which potassium sulfonate was introduced into polystyrene).
The obtained solid was subjected to elemental analysis by an oxygen flask combustion method and quantified according to JIS K 6233-1. As a result, the sulfur component in the obtained flame retardant was 7% by mass.

(D-2) In place of D-1 polystyrene, an acrylonitrile unit: 39 mol%, a styrene unit 61 mol%, a weight average molecular weight of 150,000 AS resin, and a flame retardant in which a sulfonate group is similarly introduced Obtained.
When elemental analysis was performed in the same manner as described above, the sulfur component in the obtained flame retardant was 7.1% by mass.

<Styrene resin (E) not reinforced with rubber>
(E-1) General purpose polystyrene (polystyrene 680 [registered trademark], manufactured by PS Japan, hereinafter also referred to as “E-1”) was used. Note that general-purpose polystyrene is polystyrene that does not contain a rubber component, that is, polystyrene that is not rubber-reinforced.

(E-2) Acrylonitrile-styrene resin The acrylonitrile-styrene resin (E-2) manufactured as follows was used.
A mixed liquid consisting of 4.7 parts by mass of acrylonitrile, 73.3 parts by mass of styrene, 22 parts by mass of ethylbenzene, and 0.02 parts by mass of t-butylperoxy-isopropyl carbonate as a polymerization initiator was added at 2.5 liters / hour. The polymer was continuously fed at a flow rate to a 5 liter fully mixed reactor and polymerized at 142 ° C. to obtain a polymerization solution.

  The resulting polymerization solution is continuously led to an extruder with a vent, unreacted monomers and solvent are removed under conditions of 260 ° C. and 40 Torr, the polymer is continuously cooled and solidified, and chopped into particulate acrylonitrile. -A styrene resin (hereinafter sometimes referred to as "E-2") was obtained.

  The composition of the acrylonitrile-styrene resin was analyzed by infrared absorption spectroscopy. As a result, it was 9% by mass of acrylonitrile units and 91% by mass of styrene units. The melt flow rate of acrylonitrile-styrene resin (E-2) was 78 g / 10 minutes (according to ASTM D 1238, measured at 220 ° C., 10 kg load).

<Styrenic block copolymer (F)>
(F-1) having a structure of styrene block-hydrogenated butadiene block-styrene block having a bound styrene amount of 60% by mass, a number average molecular weight Mn of 83,800, and Mw / Mn = 1.20; A styrene block copolymer (hereinafter sometimes referred to as “F-1”) having a hydrogenation rate of 99.9% was used.

  (F-2) having a structure of styrene block-hydrogenated butadiene block-styrene block having a bound styrene amount of 33% by mass, a number average molecular weight Mn of 246,000, and Mw / Mn = 1.07, A styrene block copolymer (hereinafter sometimes referred to as “F-2”) having a hydrogenation rate of 99.9% was used.

[Example 1]
95 parts by mass of polyphenylene ether (A-2), 5 parts by mass of polycarbonate (B-1), 3 parts by mass of phosphate ester flame retardant (C), flame retardant (D) 0 in which potassium sulfonate is introduced into polystyrene .3 parts by mass, ZSK25 twin-screw extruder with 10 barrels, screw diameter 25 mm, L / D = 44 (2 kneading disks L, kneading disks R: made by Werner & Pfleiderer, Germany) 6 kneading discs N: 2 screw patterns) are supplied from the most upstream part (top feed) and melt kneaded at a cylinder temperature of 300 ° C., a screw rotation speed of 250 rpm, and a vent vacuum of 7.998 kPa (60 Torr). Thus, a flame retardant resin composition was obtained. The evaluation results of the obtained flame retardant resin composition are shown in Table 1 below. L represents the distance (m) from the raw material supply port to the discharge port of the twin-screw extruder, and D represents the screw diameter (m).

[Example 2, Comparative Examples 1-7]
It mixed beforehand by the compounding ratio of Table 1, and it kneaded similarly to Example 1, and obtained the flame-retardant resin composition. The evaluation results of the obtained flame retardant resin composition are shown in Table 1 below.

  As a result of evaluation of Examples 1 and 2 and Comparative Examples 1 to 7, polyphenylene ether (A), polycarbonate (B), phosphate ester flame retardant (C), and flame retardant in which a sulfonate group is introduced into polystyrene (D ) To a specific ratio, it is possible to obtain a flame retardant resin composition that achieves heat resistance (HDT) of 120 ° C. or higher and excellent flame retardancy (V-0) and has an excellent surface appearance. I understand.

[Examples 3 to 9, Comparative Examples 8 to 11]
The mixture was mixed at the blending ratio shown in Table 2, and melt-kneaded in the same manner as in Example 1 to obtain a flame retardant resin composition. The evaluation results of the obtained flame retardant resin composition are shown in Table 2 below. “Average burning time” refers to a value obtained by dividing the total burning time described in “7. Flame retardancy” by the number of times of flame contact.

  In Examples 3 to 9 and Comparative Examples 8 to 11, the amount of the flame retardant added with a sulfonate group was examined in detail. As a result, both flame retardancy and molded appearance (white spots) were found only within the predetermined range of the present invention. It turns out that it is excellent. In Examples 4 and 9, it can be seen that there is no significant difference in flame retardancy even when the polymer component of the flame retardant into which the sulfonate is introduced is changed from polystyrene to AS resin. In addition, about average burning time, it turns out that it is a better tendency to use the flame retardant which changed the polymer component of the flame retardant which introduce | transduced the sulfonate from polystyrene to AS resin.

[Examples 10 to 19]
It mixed beforehand by the compounding ratio of Table 3 and Table 4, and it knead | mixed similarly to Example 1 and obtained the flame-retardant resin composition. The evaluation results of the obtained flame-retardant resin composition are shown in Tables 3 and 4 below. In Table 3, Example 6 is also shown for comparison.

  According to Example 10, even if (E-1) general purpose polystyrene is used as the styrene resin not containing a rubber component, (E-2) acrylonitrile-styrene resin is used for the molding fluidity of the resin composition. It can be seen that there is no significant difference compared to the case (Example 6). About glossiness, it turns out that the direction which uses acrylonitrile-styrene resin is excellent.

  According to Example 11, when (A-1) polyphenylene ether having a large intrinsic viscosity is used, the fluidity and gloss are slightly reduced, but flame retardancy and molded appearance (white spots) are satisfied.

  According to Example 12, by using the (F-1) and (F-2) styrene block copolymers, the gloss is slightly reduced, but the flame retardancy and the molded appearance (white spots) are maintained, It can be seen that the impact resistance (IZOD) is improved.

  According to Examples 13 to 19, the composition in which (A-2) a part of polyphenylene ether or (B-1) polycarbonate was replaced with (E-2) AS resin was a composition containing no AS resin. It can be seen that the die swell is suppressed and the mass productivity is excellent while maintaining the same flame retardancy.

  The polyphenylene ether / polycarbonate flame-retardant resin composition of the present invention can provide a resin composition that exhibits excellent flame retardancy, remarkably reduces white spots, has excellent molded appearance, and has high heat resistance. Furthermore, it is possible to provide a resin composition in which the balance between molding fluidity and impact resistance is improved by the combined use of a styrene block copolymer and a styrene resin. The polyphenylene ether / polycarbonate flame-retardant resin composition having these characteristics can be used extremely effectively as an extension part or reflector part for automobile lamp extension parts and various lighting fixtures.

Claims (9)

100 parts by mass of polyphenylene ether / polycarbonate resin containing 69 to 95% by mass of polyphenylene ether (A) and 5 to 31% by mass of polycarbonate (B);
3 to 10 parts by mass of phosphate ester flame retardant (C),
A flame retardant (D) 0.05 to 1.0 part by mass, which is a polystyrene and / or acrylonitrile-styrene copolymer into which a sulfonic acid group and / or a sulfonic acid group is introduced,
Polyphenylene ether / polycarbonate flame-retardant resin composition.   The styrene resin (E) not reinforced with rubber is added in an amount of 0 to 30 masses with respect to 100 mass parts in total of the component (A), the component (B), the component (C), and the component (D). The polyphenylene ether / polycarbonate flame-retardant resin composition according to claim 1, further comprising a part.   The polyphenylene ether / polycarbonate flame retardant according to claim 2, wherein the rubber-reinforced styrene resin (E) is acrylonitrile-styrene resin having an acrylonitrile unit content of 5 to 15% by mass and / or general-purpose polystyrene. Resin composition.   The styrenic block copolymer (F) is added in an amount of 0.5 to 10 mass with respect to a total of 100 mass parts of the component (A), the component (B), the component (C), and the component (D). The polyphenylene ether / polycarbonate flame-retardant resin composition according to claim 1, further comprising a part.   The polyphenylene ether according to any one of claims 1 to 4, wherein the reduced viscosity of the polyphenylene ether (A) when measured at 30 ° C using a chloroform solvent is 0.25 to 0.55 dl / g. / Polycarbonate flame retardant resin composition.   The molded object containing the polyphenylene ether / polycarbonate flame-retardant resin composition of any one of Claims 1-5.   An automotive lamp extension component comprising the polyphenylene ether / polycarbonate flame-retardant resin composition according to any one of claims 1 to 5.   An extension part of a lighting fixture comprising the polyphenylene ether / polycarbonate flame-retardant resin composition according to any one of claims 1 to 5.   The reflector component of the lighting fixture containing the polyphenylene ether / polycarbonate flame-retardant resin composition of any one of Claims 1-5.