JP5029479B2 - Flame retardant aromatic polycarbonate resin composition and molded article thereof - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention relates to an aromatic polycarbonate resin composition and an aromatic polycarbonate resin molded article having excellent flame retardancy and reduced silver during molding.

  Aromatic polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical properties, and is widely used in automobile materials, electrical / electronic equipment materials, housing materials, and the like. In particular, the flame-retardant aromatic polycarbonate resin composition is used as a member of OA / information equipment such as a computer, a notebook computer, a mobile phone, a printer, and a copying machine.

  As means for imparting flame retardancy to an aromatic polycarbonate resin, a method using a halogen-based, phosphorus-based, silicone-based, inorganic or organometallic salt-based flame retardant or flame retardant aid is known. In recent years, an organometallic salt compound that can impart flame retardancy without impairing mechanical properties such as impact resistance, heat resistance, and electrical properties inherent to aromatic polycarbonate resins, even when the amount added is relatively small. Many have been studied as useful flame retardants.

  As a technique for flame-retarding an aromatic polycarbonate with an organic metal salt compound, for example, a method using a perfluoroalkylsulfonic acid metal salt having 4 to 8 carbon atoms has been proposed (for example, see Patent Document 1). However, in this method, a perfluoroalkylsulfonic acid metal salt has an excellent flame retardant effect, but a bioaccumulative property of some perfluoroalkyl chains has been pointed out. In view of environmental considerations in recent years, flame retardant technology for aromatic polycarbonate resins using non-halogen organometallic salt compounds that do not contain halogen atoms such as chlorine, bromine, and fluorine in the molecular skeleton is strongly desired.

  Therefore, a method of adding a sodium salt of a non-halogen aromatic sulfonic acid not containing a halogen atom such as chlorine, bromine and fluorine in the molecular skeleton (see, for example, Patent Document 2), potassium of a non-halogen aromatic sulfonic acid A method of adding a salt (see, for example, Patent Document 3) and a method of adding a substituted aromatic sulfonic acid metal salt having a branched hydrocarbon group having 3 to 30 carbon atoms as a substituent (see, for example, Patent Document 4). ) Has been proposed.

  However, such an organometallic salt compound can impart flame retardancy, but it causes a decrease in the thermal stability and impact resistance of the aromatic polycarbonate resin, so there is a problem in that the amount used is limited. .

  In addition, such an organic metal salt compound generally has a hygroscopic property (deliquescent property), and therefore has a problem of low handleability. This makes accurate metering difficult when blended into an aromatic polycarbonate resin, making it difficult to stably produce a resin composition having a certain quality, particularly in production on the chemical industry scale. There existed a problem that the flame retardance of the resin composition obtained as a result varied.

  In addition, the organic metal salt compound that is deliquescent and contains a large amount of moisture in this way causes deterioration of the physical properties of the resin composition when added to the aromatic polycarbonate resin, and further, silver is generated during molding, and the appearance is impaired. There was also a problem.

  When adding an organometallic salt compound, in order to improve dispersibility, a method of adding it together with water when adding it to an aromatic polycarbonate resin has been proposed (for example, see Patent Document 5). However, when water is added and kneaded, the physical properties of the resin composition are lowered, and it is extremely difficult to suppress silver during molding. In fact, a satisfactory molded product is obtained. There was a problem that it was difficult.

JP 47-40445 A JP 2000-239509 A JP 2002-105302 A JP 2007-63529 A JP 2005-225994 A

  An object of the present invention is to provide an aromatic polycarbonate resin composition that has sufficient flame retardancy without impairing the excellent mechanical, thermal, and electrical properties of the aromatic polycarbonate resin, and has very little silver during molding. The object is to provide a product and a resin molded body formed by molding the product.

  In view of the above-mentioned problems, the inventors of the present invention, in a blend of an aromatic polycarbonate resin and an organometallic salt compound, the organic skeleton of the organometallic salt compound and the type of metal salt and flame retardancy, hygroscopicity, silver generation We studied earnestly about the relationship of influence.

  As a result, surprisingly, a salt of an aromatic sulfonic acid having a specific number of carbon atoms, specifically an aromatic ring that is unsubstituted or having a relatively small number of carbon atoms, and a specific alkali metal, specifically, In particular, the cesium (Cs) metal salt compound has a very low hygroscopic property, and exhibits excellent flame retardancy when this compound is added to an aromatic polycarbonate resin, and can suppress the generation of silver during molding. As a result, the present invention was completed.

  That is, the gist of the present invention is that the non-halogen-based resin represented by the following general formula (1) is 0.01 to 0.5 parts by weight of the fluoropolymer (B) with respect to 100 parts by weight of the aromatic polycarbonate resin (A). The present invention relates to an aromatic polycarbonate resin composition containing 0.001 to 0.5 parts by weight of an aromatic sulfonic acid cesium salt compound (C), and a resin molded product formed by molding the aromatic polycarbonate resin composition.

（式中、Ｒ_１は、水素原子、炭素数１〜１０のアルキル基を示し、Ｒ_２は水素原子、炭素数１〜７のアルキル基、炭素数６〜２０のアリールアルキル基、または炭素数５〜１５のアリール基を示し、Ｍは、セシウム（Ｃｓ）を示す。）

(In the formula, R ₁ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, or a carbon number. 5 to 15 aryl groups, and M represents cesium (Cs).

  The aromatic polycarbonate resin composition of the present invention is characterized in that it is a polycarbonate resin composition excellent in flame retardancy, reduced in silver generation during molding, and excellent in physical property balance. The aromatic polycarbonate resin composition of the present invention having such features can be expected to be applied to a wide range of fields.

  Specifically, for example, it is useful for various applications such as electrical / electronic devices and parts thereof, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. In particular, it can be expected to be applied to electrical / electronic devices, OA devices, information terminal devices, housings of home appliances, cover members, vehicle exterior / skin components, and interior components.

  Electric and electronic equipment, office automation equipment, information terminal equipment, housing for home appliances, cover members include PCs, game consoles, television display devices, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, and electronic desktops Computers, electronic dictionaries, cameras, video cameras, mobile phones, recording media drives and readers, battery packs, mice, numeric keys, CD players, MD players, portable radio / audio player housings, covers, keyboards, buttons, switches Member.

  Vehicle exterior / skin parts and interior parts include headlamps, helmet shields, inner door handles, center panels, instrument panels, console boxes, luggage floor boards, car navigation display housings, interior lighting equipment members, etc. It is done. In addition to four-wheeled vehicles, which are so-called automobiles, vehicles naturally include two-wheeled vehicles, agricultural vehicles, special vehicles for civil engineering, and railway vehicles.

  Hereinafter, the present invention will be described in more detail. In addition, the “group” possessed by various compounds means that it may have a substituent without departing from the scope of the present invention.

Aromatic polycarbonate resin (A)
Specifically, the aromatic polycarbonate resin used in the present invention is obtained by, for example, reacting an aromatic dihydroxy compound and a carbonate precursor, or a small amount of a polyhydroxy compound in combination with these. A linear or branched thermoplastic aromatic polycarbonate polymer or copolymer.

  The aromatic polycarbonate resin used in the present invention is not particularly limited, and any conventionally known one can be used. Moreover, the manufacturing method is also arbitrary and a conventionally well-known arbitrary method is employable. Specific examples include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

  Specific examples of the aromatic dihydroxy compound used as a raw material in these polycarbonate resin production methods include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) and 2,2-bis. (3,5-dibromo-4-hydroxyphenyl) propane (= tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl) -4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2 Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4- Hydroxyphenyl) -1,1,1-trichloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) ) -1,1,1,3,3,3-hexafluoropropane and other bis (hydroxyaryl) alkanes;

  Bis such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Hydroxyaryl) cycloalkanes;

  Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 4,4′-dihydroxydiphenyl ether; Dihydroxydiaryl ethers such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether;

  Dihydroxydiaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3 Dihydroxydiaryl sulfoxides such as 3,3'-dimethyldiphenyl sulfoxide;

  Examples include dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like.

  Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. These aromatic dihydroxy compounds may be used alone or in combination of two or more in any proportion.

  As the carbonate precursor to be reacted with the aromatic dihydroxy compound, carbonyl halide, carbonate ester, haloformate or the like is used. Specifically, for example, phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate;

  Dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; dihaloformate of divalent phenol and the like. These carbonate precursors may also be used alone or in combination of two or more in any proportion.

  Next, the manufacturing method of the aromatic polycarbonate resin used for this invention is demonstrated. Of the methods for producing an aromatic polycarbonate resin, the interfacial polymerization method will be described first. In this production method, the polymerization reaction is usually carried out in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and the pH is usually kept at 9 or higher, with an aromatic dihydroxy compound and, if necessary, a molecular weight modifier (end stopper). And an antioxidant for preventing oxidation of the aromatic dihydroxy compound, and after reacting with phosgene, a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added, and interfacial polymerization is carried out to obtain a polymer. Get a bonus.

  The addition of the molecular weight regulator is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction. In addition, reaction temperature is 0-40 degreeC, for example, and reaction time is several minutes (for example, 10 minutes)-several hours (for example, 6 hours), for example.

  Specific examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene. Etc .; Examples of the alkali compound used in the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

  Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group, and specifically include m-methylphenol, p-methylphenol, m-propylphenol, and p-propylphenol. -L, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. The amount of the molecular weight regulator used is preferably 50 to 0.5 mol, more preferably 30 to 1 mol, per 100 mol of the aromatic dihydroxy compound.

  Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Etc .;

  Next, the melt transesterification method will be described. The polymerization reaction in this production method is, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound. Specific examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. And substituted diphenyl carbonates. The carbonic acid diester is preferably diphenyl carbonate or substituted diphenyl carbonate, and particularly preferably diphenyl carbonate.

  Further, the aromatic polycarbonate resin used in the present invention may be appropriately adjusted by any conventionally known method because the amount of terminal hydroxyl groups greatly affects the thermal stability, hydrolysis stability, color tone and the like. In the melt transesterification reaction, usually, the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound and the degree of pressure reduction during the transesterification reaction are adjusted to obtain an aromatic polycarbonate having the desired molecular weight and terminal hydroxyl group content adjusted. Can do.

  Usually, in the melt transesterification reaction, the diester carbonate is used in an equimolar amount or more with respect to 1 mol of the aromatic dihydroxy compound, and it is preferably used in an amount of 1.01-1.30 mol. Further, as a more aggressive adjustment method, a method of adding a terminal terminator separately at the time of reaction can be mentioned, and examples of the terminal terminator used here include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters. .

  When producing polycarbonate by the melt transesterification method, a transesterification catalyst is usually used. Any conventionally known transesterification catalyst can be used. Specifically, for example, alkali metal compounds and / or alkaline earth metal compounds are preferred. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination.

  The transesterification reaction using the above raw materials is usually a reaction at a temperature of 100 to 320 ° C., and finally a melt polycondensation reaction while removing by-products such as aromatic hydroxy compounds under a reduced pressure of 2 mmHg or less. Can be done.

  The melt polycondensation can be performed by either a batch method or a continuous method. Among these, in consideration of the stability of the aromatic polycarbonate resin used in the present invention and the resin composition of the present invention, it is preferable to carry out in a continuous manner. As the catalyst deactivator used in the melt transesterification method, it is preferable to use a compound that neutralizes the transesterification reaction catalyst, such as a sulfur-containing acidic compound or a derivative formed therefrom.

  The amount of the compound that neutralizes the catalyst is preferably 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, and more preferably 1 to the polycarbonate, with respect to the alkali metal contained in the catalyst. -100 ppm, preferably 1-20 ppm.

  The molecular weight of the aromatic polycarbonate resin used in the present invention is arbitrary and may be appropriately selected and determined, but a viscosity average molecular weight [Mv] converted from the solution viscosity is preferably 10,000 to 40,000. As described above, when the viscosity average molecular weight is 10,000 or more, the mechanical strength tends to be further improved, and the viscosity average molecular weight is more preferable when used for an application requiring high mechanical strength. On the other hand, by setting it as 40000 or less, it exists in the tendency to suppress and improve a fluid fall more, and is more preferable from a viewpoint of easy moldability.

  The viscosity average molecular weight is preferably 16,000 to 40,000, particularly preferably 18,000 to 30,000. Two or more types of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed.

Here, the viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ M ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dl).

  When a branched polycarbonate is used as the polycarbonate resin used in the present invention, the production method is not particularly limited, and any conventionally known production method can be used. Specifically, for example, as described in JP-A-8-259687, JP-A-8-245782, etc., when an aromatic dihydroxy compound and a carbonic diester are reacted by a melting method (transesterification method), By selecting the catalyst conditions or the production conditions, an aromatic polycarbonate resin having a high structural viscosity index and excellent hydrolysis stability can be obtained without adding a branching agent.

  As another method, in addition to the aromatic dihydroxy compound and the carbonate precursor which are the raw materials of the polycarbonate resin described above, a trifunctional or higher polyfunctional aromatic compound is used, and the phosgene method or the melting method. (Transesterification method) includes a method of copolymerizing them.

  Specific examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl- 2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) ) Polyhydroxy compounds such as benzene, 1,1,1-tri (4-hydroxyphenyl) ethane;

  3,3-bis (4-hydroxyallyl) oxyindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred.

  The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is 0.01 to 10 mol%, particularly 0.1 to 0.1 mol, based on the aromatic dihydroxy compound. It is preferably 3 mol%.

  Specific examples of the branched structure contained in the aromatic polycarbonate resin obtained by the melting method (transesterification method) include the following general formulas (2) to (5).

（上述の一般式式（２）〜（５）において、Ｘは、単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基、または、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ−、−ＳＯ_２−で示される２価の基からなる群より選ばれるものを示す。）

(In the above general formulas (2) to (5), X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, or carbon. number 5-15 cycloalkylidene group or,, -O -, - S - , - CO -, - SO -, - SO 2 - in indicating chosen ones from the group consisting of divalent groups represented).

  The branched aromatic polycarbonate resin used in the present invention usually has a structural viscosity index N of 1.2 or more. By using this branched aromatic polycarbonate resin, a dripping prevention effect (dripping of molten resin ignited during combustion) This is preferable since the effect of preventing the increase is increased. Here, the structural viscosity index N is a value described in, for example, a known document (Shigeharu Onoki, “Rheology for chemists”, pages 15 to 16).

  The terminal hydroxyl group concentration of the aromatic polycarbonate resin used in the present invention is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, particularly preferably 600 ppm or less. Further, the lower limit is preferably 10 ppm or more, particularly 30 ppm or more, particularly 40 ppm or more in the case of an aromatic polycarbonate resin produced by a transesterification method.

  It is preferable that the terminal hydroxyl group concentration be 10 ppm or more because molecular weight reduction is suppressed and the mechanical properties of the resin composition tend to be further improved. Moreover, it is preferable for the terminal group hydroxyl group concentration to be 1000 ppm or less because the residence heat stability and color tone of the resin composition tend to be further improved.

  In addition, the unit of the terminal hydroxyl group density | concentration is what displayed the weight of the terminal hydroxyl group with respect to the weight of aromatic polycarbonate resin in ppm, and the measuring method is the colorimetric determination (Macromol. Chem. 88 215) by a titanium tetrachloride / acetic acid method. (Method of (1965)).

  The aromatic polycarbonate resin used in the present invention is not limited to a polycarbonate resin alone (a polycarbonate resin alone is an embodiment containing only one type of polycarbonate resin, and includes, for example, a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. In addition to an alloy (mixture) of a polycarbonate resin and another thermoplastic resin, for example, an oligomer having a siloxane structure for the purpose of further improving the flame retardancy, which is the object of the present invention, or A copolymer mainly composed of a polycarbonate resin, such as a copolymer with a polymer, is also included.

  In addition, the aromatic polycarbonate resin used in the present invention may contain an aromatic polycarbonate oligomer in order to improve the appearance of the molded product and the fluidity. The viscosity average molecular weight [Mv] of the aromatic polycarbonate oligomer is preferably 1500 to 9500, particularly preferably 2000 to 9000. The aromatic polycarbonate oligomer is preferably 30% by weight or less of the aromatic polycarbonate resin.

  In the alloy or copolymer of the aromatic polycarbonate resin, the content of another thermoplastic resin (the block portion in the case of the copolymer) with respect to 100 parts by weight of the aromatic polycarbonate resin used in the present invention is 100% by weight. Part or less, particularly 70 parts by weight or less, more preferably 60 parts by weight or less, and particularly preferably 50 parts by weight or less. Other thermoplastic resins other than polycarbonate resin include polyester resins such as polybutylene terephthalate and polyethylene terephthalate, styrene resins such as polyamide resin, HIPS resin and ABS resin, polyolefin resins such as polyethylene and polypropylene, and the like. . Of these, styrene resins are preferable, and ABS resins are particularly preferable.

  Furthermore, as the aromatic polycarbonate resin used in the present invention, not only virgin raw materials but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins may be used. Used products include 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, waves, etc. A building member such as a plate is preferred.

  Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less, among the aromatic polycarbonate resins used in the present invention.

Fluoropolymer (B)
In the present invention, as the fluoropolymer, any conventionally known fluoropolymer can be used and may be appropriately selected and determined. Of these, fluoroolefin resins are preferred. As the fluoroolefin resin, a polymer or copolymer containing a fluoroethylene structure is usually used. Specifically, for example, difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like are used. Can be mentioned. Among these, tetrafluoroethylene resin and the like are preferable, and as this fluoroethylene resin, a fluoroethylene resin having fibril forming ability is preferable.

  Specific examples of the fluoroethylene resin having fibril-forming ability used in the present invention include Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Polyflon F201L manufactured by Daikin Chemical Industries, and Polyflon F103. . Examples of the aqueous dispersion of fluoroethylene resin include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and Fullon D-1 manufactured by Daikin Chemical Industries. Furthermore, in the present invention, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used, and specific examples include METABRENE A-3800 manufactured by Mitsubishi Rayon Co., Ltd.

  Content of the fluoropolymer (B) in this invention is 0.001-0.5 weight part with respect to 100 weight part of aromatic polycarbonate resin (A). If the content of the fluoropolymer (B) is too small, the flame retardancy of the resulting polycarbonate resin composition becomes insufficient. On the other hand, if the content is too large, the heat resistance is remarkably reduced, or the appearance of the polycarbonate resin molded product is poor. Mechanical strength may decrease.

  Therefore, it is preferable that content of the fluoropolymer (B) in this invention is 0.005-0.45 weight part especially with respect to 100 weight part of polycarbonate resin (A), Furthermore, 0.01-0. It is preferably 4 parts by weight, particularly 0.1 to 0.35 parts by weight.

Non-halogen aromatic sulfonic acid cesium salt compound (C)
The non-halogen aromatic sulfonic acid cesium salt compound (C) used in the present invention is represented by the following general formula (1), and is characterized by using cesium as a metal element forming a salt.

（式中、Ｒ_１は、水素原子、炭素数１〜１０のアルキル基を示し、Ｒ_２は水素原子、炭素数１〜７のアルキル基、炭素数６〜２０のアラルキル基、または炭素数５〜１５のアリール基を示し、Ｍは、セシウム（Ｃｓ）を示す。）

(In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or 5 carbon atoms. -15 represents an aryl group, and M represents cesium (Cs).

  This is because, by using cesium as the metal element M in the non-halogen type aromatic sulfonic acid metal salt, cesium has a high catalytic effect on the aromatic polycarbonate resin, even if the addition amount is small, char formation during combustion It is considered that the performance is effectively exhibited and excellent flame retardancy is obtained. Furthermore, it is considered that the use of the cesium salt tends to reduce the hygroscopicity of the resin composition and to reduce the silver during molding of the resulting aromatic polycarbonate resin composition.

  In the present invention, flame retardancy can be further improved by lowering the carbon number of the substituent in the aromatic ring of the aromatic sulfonic acid moiety constituting the non-halogen aromatic sulfonic acid metal salt compound (C). It is characterized by. In the present invention, it is important to use a non-halogen type aromatic sulfonic acid metal salt compound in which both the structure of the aromatic sulfonic acid moiety and the metal element are specified.

In the non-halogen aromatic sulfonic acid cesium salt compound (C) represented by the general formula (1) used in the present invention, a hydrocarbon having a small number of carbon atoms as R ¹ is located in the para position with respect to the sulfonic acid group. It has a group. R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. Specific examples of R ¹ include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group. Among them, the carbon number is 5 or less, further 3 or less, especially 1 carbon atom. It is preferably an alkyl group (methyl group).

The non-halogen aromatic sulfonic acid cesium salt compound (C) represented by the general formula (1) used in the present invention has R ² in addition to R ¹ as a substituent in the aromatic ring. , R ² represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or an aryl group having 5 to 15 carbon atoms.

Specific examples of the alkyl group in R ² are the same as those in R ₁ , and examples of the aralkyl group include those in which a part of hydrogen atoms of the alkyl group is substituted with an aryl group. Specific examples of the aryl group include an unsubstituted or substituted phenyl group; a naphthyl group, and the like. In addition, these aralkyl groups and aryl groups may contain a hetero atom.

As the non-halogen aromatic sulfonic acid metal salt compound (C) used in the present invention, in R ¹ and R ² described above, R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom. The alkyl group represented by R ¹ is preferably an alkyl group (methyl group) having 5 or less carbon atoms, more preferably 3 or less, and particularly 1 carbon atom.

  Specific examples of the non-halogen aromatic sulfonic acid metal salt compound used in the present invention include, for example, benzenesulfonic acid; 2-toluenesulfonic acid, 3-toluenesulfonic acid, and 4-toluene as the aromatic sulfonic acid moiety. Toluene sulfonic acids such as sulfonic acid; xylene-4-sulfonic acids such as o-xylene-4-sulfonic acid and m-xylene-4-sulfonic acid; 3-nitrobenzenesulfonic acid; p-styrenesulfonic acid; Examples include cesium salts, and anhydrides and hydrates thereof.

  Among these, the aromatic sulfonic acid moiety is preferably benzenesulfonic acid or toluenesulfonic acids. As the non-halogen-based aromatic sulfonic acid cesium salt compound (C) used in the present invention, among them, cesium benzenesulfonate and cesium toluenesulfonate are preferable, and cesium 4-toluenesulfonate is particularly preferable.

  The pH of the non-halogen-based aromatic sulfonic acid cesium salt compound (C) used in the present invention is not particularly limited, but is usually 4 to 8, particularly 5 to 7, particularly 5.5 to 6.8. Is preferred. Content of the non-halogen-type aromatic sulfonic acid cesium salt compound (C) in this invention is 0.001-0.5 weight part with respect to 100 weight part of aromatic polycarbonate resin (A), Especially 0.005 It is preferable that it is -0.3 weight part, Furthermore, it is 0.01-0.2 weight part, It is especially preferable that it is 0.02-0.1 weight part.

  When the content of the non-halogen aromatic sulfonic acid cesium salt compound (C) is less than 0.001 part by weight, the flame retardant effect is insufficient, and when it exceeds 0.5 part by weight, the effect reaches a peak, Thermophysical properties such as molecular weight reduction and mechanical properties may decrease, and in some cases, flame retardancy may decrease.

Other components The flame retardant aromatic polycarbonate resin composition of the present invention, if necessary, within a range not impairing various physical properties such as flame retardancy, transparency, hue, and thermal stability, which are the effects of the present invention, Other resins and various resin additives may be contained.

  Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), Styrene resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin); polyethylene resin Polyolefin resins such as polypropylene resins; Polyamide resins; Polyimide resins; Polyetherimide resins; Polyurethane resins; Polyphenylene ether resins; Polyphenylene sulfide resins Polysulfone resins; polymethacrylate resins, and the like. These may be used in combination of two or more types may be used alone.

  Further, as various resin additives, any conventionally known additives may be appropriately selected and used within a range not impairing the effects of the present invention. Specifically, for example, heat stabilizers, antioxidants, mold release agents, etc. UV absorbers, dyes and pigments, flame retardants, anti-dripping agents, antistatic agents, antifogging agents, lubricants / antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. Two or more of these may be used in combination.

  Examples of the heat stabilizer include phosphorus compounds. As the phosphorus compound, any conventionally known compound can be used. Specifically, for example, phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like. Among these, the organic phosphate compound represented by the following general formula (6) and / or the organic phosphite compound represented by the following general formula (7) are preferable.

O = P (OH) _m (OR) _3-m (6)
(In the above formula, R represents an alkyl group or an aryl group, which may be the same or different, and m represents an integer of 0 to 2.)

（式中、Ｒ’はアルキル基またはアリール基を示し、それぞれ同一でも、異なっていてもよい。）

(In the formula, R ′ represents an alkyl group or an aryl group, which may be the same or different.)

  In general formula (6), R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and particularly preferably an alkyl group having 2 to 25 carbon atoms. M is preferably 1 or 2.

  In general formula (7), R ′ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Preferable specific examples of the organic phosphite represented by the general formula (7) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

  The content of these phosphorus compounds is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the aromatic polycarbonate resin, particularly 0.01 to 0.7 parts by weight, particularly 0.03 to 0 parts. .5 parts by weight is preferred.

  Examples of the antioxidant include hindered phenol antioxidants. Specifically, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert -Butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Len-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, etc. These may be used in combination of two or more.

  Among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate is preferred. These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.

  The content of the antioxidant is usually 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the aromatic polycarbonate resin. If the content of the antioxidant is too small, the effect is insufficient. On the contrary, if the content is too large, the effect reaches its peak and is not economical. Specific examples of the release agent include aliphatic carboxylic acids and alcohol esters thereof, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, polysiloxane silicone oil, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated, linear or cyclic aliphatic 1 to 3 carboxylic acids. Among these, monovalent or divalent carboxylic acids having 6 to 36 carbon atoms are preferable, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are particularly preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, and montanic acid. , Adipic acid, azelaic acid and the like.

  As the aliphatic carboxylic acid in the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. Examples of the alcohol moiety of the ester include saturated or unsaturated, linear or cyclic, monovalent or polyhydric alcohols, which may have a substituent such as a fluorine atom or an aryl group. Among these, a valent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and a saturated aliphatic monovalent or polyhydric alcohol having 30 or less carbon atoms and saturated aliphatic alcohol is particularly preferable.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaol. Examples include erythritol. The aliphatic carboxylic acid ester may contain an aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a plurality of aliphatic carboxylic acid esters.

  Specific examples of the aliphatic carboxylic acid ester include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin diester. Examples thereof include stearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Moreover, these hydrocarbon compounds may be partially oxidized.

  Among these aliphatic hydrocarbons, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are particularly preferable. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

  Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, fluorinated alkyl silicone, and the like, and these may be used alone or in combination of two or more.

  The content of the release agent in the present invention is usually 0.001 to 2 parts by weight, preferably 0.01 to 1 part by weight, with respect to 100 parts by weight of the aromatic polycarbonate resin. If the content of the release agent is too low, the release effect is not sufficiently exhibited. Conversely, if the content is too high, degradation of the hydrolysis resistance of the aromatic polycarbonate resin or mold contamination during injection molding occurs. There is a case.

  Specific examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, and organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds. Among them, organic ultraviolet absorbers are preferable. In particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- ON], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

  Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- Benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. These may be used alone or in combination of two or more at any ratio.

  Among these benzotriazole compounds, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H -Benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6 -(2N-benzotriazol-2-yl) phenol] and the like are preferable.

  Content of the ultraviolet absorber in this invention is 0.01-3 weight part normally with respect to 100 weight part of aromatic polycarbonate resin, Preferably it is 0.1-1 weight part. If the content of the ultraviolet absorber is too small, the effect of improving the weather resistance may be insufficient. Conversely, if the content is too large, problems such as mold deposit may occur.

  Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes. Inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc -Oxide pigments such as iron-based brown, titanium-cobalt-based green, cobalt-green, cobalt-blue, copper-chromium-based black, copper-iron-based black; chromic acid such as chrome, molybdate orange Pigments: ferrocyan pigments such as bitumen.

  Organic pigments and organic dyes include: phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine And condensed polycyclic dyes such as isoindolinone and quinophthalone; anthraquinone, heterocyclic, and methyl dyes.

  These may be used alone or in combination of two or more at any ratio, and from the viewpoint of thermal stability, titanium oxide, carbon black, cyanine series, quinoline series, anthraquinone series, phthalocyanine series compounds and the like are preferable. .

  The content of the dye / pigment is usually 5 parts by weight or less, particularly 3 parts by weight or less, and particularly preferably 2 parts by weight or less with respect to 100 parts by weight of the aromatic polycarbonate resin. If the content of the dye / pigment is too large, the impact resistance may be significantly reduced.

  Any conventionally known flame retardant can be used. Specifically, for example, halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardant such as brominated polystyrene, phosphate ester flame retardant, organometallic salt flame retardant , Silicone flame retardants, inorganic compound flame retardant (auxiliary) agents, and the like. These may be used alone or in combination of two or more at any ratio. Among these, organometallic salt flame retardants, silicone flame retardants, and inorganic compound flame retardants (auxiliaries) that have a very low possibility of environmental pollution are preferable.

  Examples of the organic metal salt flame retardant include dipotassium diphenylsulfone-3,3′-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, (Branched) sodium dodecylbenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, (poly) potassium styrenesulfonate, potassium paratoluenesulfonate, (branched) potassium dodecylbenzenesulfonate, potassium perfluorobutanesulfonate Can be mentioned.

  Examples of the inorganic compound flame retardant (auxiliary) agent include talc, mica, kaolin, clay, silica powder, fumed silica, and glass flakes.

  The content of the flame retardant in the present invention is usually 0.0001 to 30 parts by weight, particularly 0.01 to 25 parts by weight, particularly 0.1 to 20 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. Preferably there is. If the content of the flame retardant is too small, the flame retardant effect becomes insufficient. Conversely, if the content is too large, the thermal stability and heat resistance may be significantly reduced.

Production of Flame Retardant Aromatic Polycarbonate Resin Composition The flame retardant aromatic polycarbonate resin composition of the present invention contains a specific amount of the above-mentioned non-halogen aromatic sulfonic acid cesium salt compound in an aromatic polycarbonate or fluoropolymer. It is characterized by that. And the manufacturing method in particular is not restrict | limited, What is necessary is just to select and select suitably from the conventionally well-known arbitrary manufacturing methods of a resin composition.

  Specifically, the method for producing the flame-retardant aromatic polycarbonate resin composition of the present invention includes, for example, the above-described aromatic polycarbonate, a metal salt compound component, and, if necessary, other additive components, tumbler or Henschel. Examples include a method of premixing using various mixers such as a mixer and then melt-kneading with a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. It is done.

  Alternatively, the resin composition may be produced by mixing each component in advance, or by mixing only a part of the components in advance, supplying the mixture to an extruder using a feeder, and melt-kneading the mixture. Furthermore, a resin composition obtained by mixing some components in advance, supplying them to an extruder and melt-kneading is used as a master batch, and the resin composition is manufactured by mixing again with other components and melt-kneading. You can also

  In particular, in the method for producing a flame-retardant aromatic polycarbonate resin composition of the present invention, the above-described non-halogen-based aromatic sulfonic acid metal salt compound is masterbatched with a resin component in advance to produce a resin composition. , Dispersibility, and further, extrusion workability is improved, which is preferable. In addition, from the viewpoint of improving the dispersibility of the above-mentioned non-halogen aromatic sulfonic acid cesium salt compound, it is also effective to knead after dissolving it in a solvent such as an organic solvent in advance.

Flame Retardant Aromatic Polycarbonate Resin Molded Body and Method for Producing the Same The flame retardant aromatic polycarbonate resin molded body of the present invention is the above-described flame retardant aromatic polycarbonate resin composition of the present invention. It can be obtained by resin molding. The manufacturing method of a resin molding is not specifically limited, The conventionally well-known arbitrary shaping | molding methods generally used about a thermoplastic resin can be used.

  Specific examples of the resin molding method include a press molding method, a transfer molding method, an extrusion molding method, a vacuum molding method, a blow molding method, and an injection molding method. Among them, in the present invention, it is preferable to use an injection molding method.

  The flame-retardant aromatic polycarbonate resin molded article obtained by the injection molding method using the resin composition of the present invention is obtained with high production efficiency, which is a feature of the injection molding method, and is characterized by the aromatic polycarbonate resin. It has excellent flame retardancy without impairing certain excellent mechanical, thermal, and electrical characteristics, and it is excellent in that it has very little silver during molding.

  Specific examples of the injection molding method include, for example, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow injection molding method such as gas assist, metal parts by insert injection molding method, and other parts. Examples thereof include an integral molding method, a two-color injection molding method, a core back injection molding method, and a sandwich injection molding method. As the mold used in such an injection molding method, any conventionally known mold can be used. Specific examples include a heat insulating mold and a rapid heating mold.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples, unless the summary is exceeded. “Part” means “part by weight”.

Reference Examples 1-5
Hygroscopic evaluation 10 g of organometallic salt compounds (C-1 to C-5) are put in a petri dish and left to stand in an atmosphere of 20 ° C. × 65% RH. Every predetermined time (0 to 48 h), Karl Fischer moisture meter The moisture value was measured. A larger (unit wt%) value indicates lower hygroscopicity and better handleability when blended with an aromatic polycarbonate resin.

Example 1 and Comparative Examples 1-5
Resin pellet production Each component described in Table 2 was blended in the ratio (weight ratio) described in Table 4, mixed for 20 minutes with a tumbler, and then a 40 mm single screw extruder manufactured by Tanabe Seiki Co., Ltd. equipped with 1 vent ( VS-40), the molten resin kneaded at 280 ° C. and extruded into a strand shape was quenched in a water bath and pelletized using a pelletizer. In addition, the addition amount of the organometallic salt compounds (C-1 to C-6) in Table 4 was adjusted to a ratio of 1.5 to 2.4 mmol of the organometallic salt compound per 1000 g of the polycarbonate resin composition.

Preparation of UL Test Specimen Pellets obtained by the above production method were dried at 120 ° C. for 5 hours, and then a cylinder temperature of 290 ° C. and a mold temperature of 80 using a J50-EP injection molding machine manufactured by Nippon Steel. A test piece having a length of 125 mm, a width of 13 mm, and a thickness of 1.58 mm was formed by injection molding under the conditions of ° C and a molding cycle of 30 seconds.

Next, an evaluation method for each aromatic polycarbonate resin will be described.
Flammability test UL test samples are conditioned for 48 hours in a temperature-controlled room at 23 ° C and 50% humidity. Difficult to comply with UL94 test (combustion test of plastic materials for equipment parts) established by UL Flammability was evaluated. UL94V is a method for evaluating flame retardancy from the afterflame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically. In order to have the property, it is necessary to satisfy the criteria shown in Table 1 below.

  Here, the afterflame time is the length of time for which the test piece continues to be flammable after the ignition source has been moved away, and the drip cotton ignition is a mark approximately 300 mm below the lower end of the test piece. This is determined by whether the cotton used is ignited by a drip from the specimen. Moreover, when one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied.

Surface appearance The state of the surface appearance (silver streak state) of the above-mentioned test piece having a length of 125 mm, a width of 13 mm, and a thickness of 1.58 mm was visually observed, and “○” indicates that almost no silver streak was observed. The case where silver streak was observed was designated as “x”.

Claims (4)

Non-halogen aromatic sulfonic acid cesium salt compound represented by 0.001 to 0.5 parts by weight of fluoropolymer (B) and the following general formula (1) with respect to 100 parts by weight of aromatic polycarbonate resin (A) A flame-retardant aromatic polycarbonate resin composition comprising 0.001 to 0.5 parts by weight of (C).

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, or a carbon number. 5 to 15 aryl groups, and M represents cesium (Cs). The flame retardant aromatic polycarbonate resin composition according to claim 1, wherein R ² in the non-halogen aromatic sulfonic acid cesium salt compound (C) represented by the general formula (1) is a hydrogen atom. object.   The flame retardant aromatic polycarbonate resin composition according to claim 1 or 2, wherein the non-halogen aromatic sulfonic acid cesium salt compound (C) is cesium p-toluenesulfonate.   A flame-retardant aromatic polycarbonate resin molded article obtained by injection molding the flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 3.