JP4697416B2 - Flame retardant polycarbonate resin composition and molded product thereof - Google Patents

Description

  The present invention relates to a flame retardant polycarbonate resin composition and a molded product thereof. More specifically, it exhibits good flame retardancy and excellent mechanical strength and transparency without containing halogen-based flame retardants or phosphorus-based flame retardants containing bromine, chlorine, etc. that cause environmental pollution. The present invention relates to a flame retardant polycarbonate resin composition and a molded product thereof.

  Polycarbonate resin is widely used industrially in the automotive field, OA equipment field, electrical / electronic field, etc., but the resin material used is made flame retardant mainly in applications such as OA equipment, electrical / electronic products. There are strong demands, and many flame retardants are being developed and studied in order to meet these demands. Conventionally, brominated compounds are used exclusively for flame retarding polycarbonate resins, or antimony trioxide is used in combination therewith. However, such a resin composition has a problem that it generates bromine gas during combustion and causes environmental pollution. In recent years, it has been reported that phosphorus flame retardants such as phosphate esters are used in combination with bromine compounds or used alone for the purpose of reducing the amount of bromine compounds used. However, phosphorus flame retardants decompose when used. Thus, the resin composition has the disadvantage of lowering the mechanical strength and does not completely eliminate the environmental pollution problem.

  Non-phosphorous flame retardant materials or non-phosphorous / non-brominated flame retardant materials, for example, flame retardants comprising an organic acid salt of an alkali metal or alkaline earth metal such as a sulfonate, polytetrafluoroethylene and an aromatic polycarbonate Flame retardant polycarbonate resin composition comprising a polycarbonate resin composition (Patent Document 1: Japanese Patent Application Laid-Open No. 51-045159) and an alkali metal salt or alkaline earth metal salt of a polycarbonate and perfluoroalkanesulfonic acid and an epoxy resin (Patent Document 2: JP 06-073281 A), a flame retardant polycarbonate resin composition comprising a polycarbonate resin, a metal salt of an aromatic sulfur compound, a fiber-forming fluorine-containing polymer and an organopolysiloxane (Patent Document 3: Japanese Patent Laid-Open No. 2004-155938) has been proposed. However, in the case of the flame retardant polycarbonate resin composition as described above, not only is the transparency characteristic of the polycarbonate resin impaired, but if a sufficient amount of flame retardant is blended to express flame retardancy, the resin composition The melt heat stability of the product is impaired, yellowing of the molded product, the occurrence of silver, and the mechanical strength is significantly reduced.

  In addition, the aromatic monomer unit having a sulfonic acid group in the aromatic skeleton is composed of 15 to 45 mol% of a styrene polymer sulfonic acid metal salt with respect to the total monomer units, and the content of the metal sulfate is 5 A flame-retardant resin composition (Patent Document 4: Japanese Patent Application Laid-Open No. 2003-064229) composed of a styrene polymer and a polycarbonate having a mass% of less is also proposed, but this is poor in thermal stability and easily yellows. The weather resistance was also unsatisfactory. Furthermore, a flame retardant resin composition comprising an aromatic polycarbonate resin, a styrene resin, an organic alkali metal salt and / or an organic alkaline earth metal salt, and a functional group-containing silicone compound (Patent Document 5: Japanese Patent Application Laid-Open No. 2004-035587) ) Is also proposed, but it is a flame-retardant resin composition having low gloss and weld tensile elongation and low practicality.

  In the case of a resin composition containing a flame retardant that does not contain halogen or phosphorus as described above, if the flame retardant is insufficient, or if a sufficient amount of flame retardant is added to express the flame retardant, The melt heat stability of the resin composition is impaired, the molded product is yellowed, and the mechanical strength is significantly reduced.

JP 51-045159 A Japanese Patent Application Laid-Open No. 06-073281 JP 2004-155938 A JP 2003-064229 A Japanese Patent Laid-Open No. 2004-035587

  The object of the present invention is to satisfy the severe flame retardant level equivalent to the case where these flame retardants are used without using halogen-based or phosphorus-based flame retardants that cause environmental pollution or performance deterioration, and An object of the present invention is to provide a flame retardant polycarbonate resin composition excellent in mechanical strength, thermal stability, transparency and the like, and a molded product thereof.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition in which a small amount of a novel polyphenylene ether (hereinafter abbreviated as PPE) oligomer sulfonate is blended with a polycarbonate resin is polycarbonate. Severe flame retardant levels are achieved by forming a large amount of carbide during resin combustion, covering the surface of the resin where the carbide is burning, and delaying the supply of cracked gas generated inside the resin to the combustion field I found out that I can do it. In addition, the novel PPE oligomer sulfonate has good compatibility with the polycarbonate resin, so it has been found that it has excellent mechanical strength and transparency even when blended with the polycarbonate resin. I let you.

  That is, in the present invention, 0.01 to 3.0 parts by mass of the sulfonic acid alkali metal salt or sulfonic acid alkaline earth metal salt of the PPE oligomer represented by the following structural formula (1) with respect to 100 parts by mass of the polycarbonate resin. Provided are a flame retardant polycarbonate resin composition obtained by blending and a molded product obtained by molding the flame retardant polycarbonate resin composition.

（式中、−（Ｏ−Ｘ−Ｏ）−は、構造式（２）で示され、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁸、Ｒ⁹は、同一又は異なってもよく、ハロゲン原子、炭素数６以下のアルキル基又はフェニル基である。Ｒ⁵、Ｒ⁶、Ｒ⁷は、同一又は異なってもよく、水素原子、ハロゲン原子、炭素数６以下のアルキル基又はフェニル基である。−（Ｙ−Ｏ）−は、構造式（３）で定義される１種類の構造、又は構造式（３）で定義される２種類以上の構造がランダムに配列したものである。Ｒ¹⁰、Ｒ¹¹は、同一又は異なってもよく、ハロゲン原子、炭素数６以下のアルキル基又はフェニル基である。Ｒ¹²、Ｒ¹³は、同一又は異なってもよく、水素原子、ハロゲン原子、炭素数６以下のアルキル基又はフェニル基である。Ｚは、炭素数１〜６の２価の有機基であり、酸素原子を含んでいてもよい。Ｒ¹は構造式（４）で示される基を必須に有するものであるが、Ｒ¹の一部が水素原子又はグリシジル基であってもよく、Ｍはアルカリ金属及び／又はアルカリ土類金属である。ａ、ｂは０〜１００の整数を示す。ｃ、ｄは０〜２０の整数を示す。）

(In the formula, — (O—X—O) — is represented by the structural formula (2), and R ² , R ³ , R ⁴ , R ⁸ and R ⁹ may be the same or different, and may be a halogen atom, R ⁵ , R ⁶ , and R ⁷ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. (Y-O) - is one in which one kind of structure defined, or two or more kinds of structures defined by the formula (3) are arranged in a random structure (3) .R ^10, R ¹¹ may be the same or different, and is a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R ¹² and R ¹³ may be the same or different, and are a hydrogen atom, a halogen atom, or 6 or less carbon atoms. Z is a divalent organic group having 1 to 6 carbon atoms, and is an oxygen atom. Although may contain a .R ¹ are those having a group represented by the structural formula (4) mandatory, part of R ¹ may be hydrogen atom or a glycidyl group, M is an alkali metal and (It is an alkaline earth metal. A and b represent an integer of 0 to 100. c and d represent an integer of 0 to 20.)

  The flame-retardant polycarbonate resin composition and molded product thereof according to the present invention are flame-retardant materials using a small amount of non-phosphorus and non-bromine flame retardants, and are excellent in mechanical strength, transparency, and thermal stability, and have severe difficulties. Since it meets the fuel level, it is ideal for various applications, especially for electrical / electronic / OA equipment parts and precision parts.

Hereinafter, the present invention will be described in detail.
The polycarbonate resin used in the present invention may be a branched heat prepared by reacting an aromatic dihydroxy compound or a mixture of an aromatic dihydroxy compound and a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester. Mention may be made of homopolymers or copolymers of plastic aromatic polycarbonates. As a polymerization method for preparing the aromatic polycarbonate resin, methods such as an interfacial polycondensation method (phosgenation method) and a melt polymerization method (transesterification method) can be employed.

  As raw material aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol and 4 , 4'-dihydroxydiphenyl and the like, or two or more selected from bisphenol A are preferable. To obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 1,3,5-tris (4-hydroxyphenyl) benzene and 1,1 , 1-tris (4-hydroxyphenyl) ethane, or other polyhydroxy compounds, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichloro Luisatin bisphenol or 5-bromoisatin bisphenol together with the aromatic dihydroxy compound May be placed, the amount of these compounds is from 0.01 to 10 mol% based on the total amount of the aromatic dihydroxy compound and a polyhydroxy compound, preferably from 0.1 to 2 mol%.

  The molecular weight of the polycarbonate resin is the same as that of the polycarbonate resin, that is, in the presence of the polymerization catalyst, the quantitative ratio of the aromatic dihydroxy compound and the alkaline aqueous solution of the monovalent aromatic hydroxy compound as a terminal terminator and the carbonyl halide compound. It can be adjusted by supplying it into an organic solvent and polymerizing it. Examples of the monovalent aromatic hydroxy compound used as a terminal terminator include m- or p-methylphenol, m- or p-propylphenol, p-tert-butylphenol, or a long-chain alkyl-substituted phenol. The polycarbonate resin is preferably derived from a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane or 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy compound. And a polycarbonate copolymer. Further, the resin may be a polymer having a siloxane structure, and for example, an oligomer having a siloxane structure can be copolymerized for the purpose of enhancing flame retardancy. The molecular weight of the polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 15,000 to 40,000, more preferably 16,000 to 30. , 000.

  The sulfonic acid alkali metal salt or sulfonic acid alkaline earth metal salt of the PPE oligomer used in the present invention is represented by the following structural formula (1).

（式中、−（Ｏ−Ｘ−Ｏ）−は、構造式（２）で示され、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁸、Ｒ⁹は、同一又は異なってもよく、ハロゲン原子、炭素数６以下のアルキル基又はフェニル基である。Ｒ⁵、Ｒ⁶、Ｒ⁷は、同一又は異なってもよく、水素原子、ハロゲン原子、炭素数６以下のアルキル基又はフェニル基である。−（Ｙ−Ｏ）−は、構造式（３）で定義される１種類の構造、又は構造式（３）で定義される２種類以上の構造がランダムに配列したものである。Ｒ¹⁰、Ｒ¹¹は、同一又は異なってもよく、ハロゲン原子、炭素数６以下のアルキル基又はフェニル基である。Ｒ¹²、Ｒ¹³は、同一又は異なってもよく、水素原子、ハロゲン原子、炭素数６以下のアルキル基又はフェニル基である。Ｚは、炭素数１〜６の２価の有機基であり、酸素原子を含んでいてもよい。Ｒ¹は構造式（４）で示される基を必須に有するものであるが、Ｒ¹の一部が水素原子又はグリシジル基であってもよく、Ｍはアルカリ金属及び／又はアルカリ土類金属である。ａ、ｂは０〜１００の整数を示す。ｃ、ｄは０〜２０の整数を示す。）

(In the formula, — (O—X—O) — is represented by the structural formula (2), and R ² , R ³ , R ⁴ , R ⁸ and R ⁹ may be the same or different, and may be a halogen atom, R ⁵ , R ⁶ , and R ⁷ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. (Y-O) - is one in which one kind of structure defined, or two or more kinds of structures defined by the formula (3) are arranged in a random structure (3) .R ^10, R ¹¹ may be the same or different, and is a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R ¹² and R ¹³ may be the same or different, and are a hydrogen atom, a halogen atom, or 6 or less carbon atoms. Z is a divalent organic group having 1 to 6 carbon atoms, and is an oxygen atom. Although may contain a .R ¹ are those having a group represented by the structural formula (4) mandatory, part of R ¹ may be hydrogen atom or a glycidyl group, M is an alkali metal and (It is an alkaline earth metal. A and b represent an integer of 0 to 100. c and d represent an integer of 0 to 20.)

Here, examples of the halogen atom in R ^{2 to} R ¹³ include chlorine, bromine, and fluorine, and examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group. Preferably, in — (O—X—O) — in the structural formula (2), R ² , R ³ , R ⁴ , R ⁸ and R ⁹ are each an alkyl group having 3 or less carbon atoms, R ⁵ , R ⁶ and R ⁷ are a hydrogen atom or an alkyl group having 3 or less carbon atoms. In — (YO) — in the structural formula (3), R ¹⁰ and R ¹¹ are alkyl groups having 3 or less carbon atoms, R ¹² , R ¹³ is a hydrogen atom or an alkyl group having 3 or less carbon atoms.

Particularly preferably, in — (O—X—O) — in the structural formula (2), R ² , R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ are methyl groups, and R ⁵ and R ⁶ are hydrogen atoms. In the structure represented by the following structural formula (5) and-(YO)-in the structural formula (3), R ¹⁰ and R ¹¹ are methyl groups, R ¹² is a hydrogen atom or a methyl group, R ^{The following} structural formula (6) or structural formula (7), wherein ¹³ is a hydrogen atom, or a polyphenylene ether oligomer alkali metal sulfonate having a structure in which structural formula (6) and structural formula (7) are randomly arranged Salts or alkaline earth metal sulfonates.

Moreover, as a C1-C6 bivalent organic group which may contain the oxygen atom of-(Z)-, alkylene groups, such as a methylene group, ethylene group, a propylene group, a butylene group, a hexylene group, etc., etc. In these alkylene groups, —O— may be interposed or bonded to the R ¹ side terminal.

In addition, Preferably 50-100 mol% of R < ¹ >, More preferably, 80-100 mol% is group shown by the said Structural formula (4), The remainder is a hydrogen atom or a glycidyl group. M is an alkali metal or an alkaline earth metal such as magnesium, calcium or barium, but is preferably sodium and / or potassium. In a and b, a + b is preferably 0 to 50, particularly preferably a + b is 0 to 10, and c and d are preferably 0 to 10, particularly preferably 0.

  The polyphenylene ether oligomer sulfonate manufacturing method of the present invention uses a polyphenylene ether oligomer containing both end epoxy groups represented by the following structural formula (8). A bifunctional polyphenylene ether oligomer having an epoxy group at the terminal (hereinafter referred to as OPE-2Gly) is a bifunctional polyphenylene ether oligomer represented by the structural formula (9) or (10). It is obtained by dehydrohalogenation reaction in the presence of a glycidyl halide such as epichlorohydrin and a base.

（式中、ａ、ｂ、ｃ、ｄ、並びにＺ、及びＲ²〜Ｒ¹³は、前記の通り。）

(Wherein a, b, c, d, and Z, and R ^{2 to} R ¹³ are as described above.)

  The bifunctional OPE used in the present invention is not particularly limited as long as it has a structure represented by Structural Formula (9) or Structural Formula (10). The bifunctional OPE represented by the structural formula (9) can be obtained, for example, by a method of copolymerizing a divalent phenol and a monovalent phenol in the presence of an amine described in JP-A-2003-12796. it can.

Incidentally, - (Z) - as, for _{example, - (CH 2) m O} -, - (CH 2 CHR 14 O) - was introduced, a method for producing the bifunctional OPE represented by the structural formula (10) explain. In the case of — (CH ₂ ) _m O—, the bifunctional OPE represented by the structural formula (9) and the halogenated alcohol represented by the structural formula (11) are mixed with an appropriate solvent such as alcohol, ether, or ketone. It can be introduced by reacting in the presence of an alkali metal salt such as potassium hydroxide, potassium carbonate, sodium ethoxide. In the case of — (CH ₂ CHR ¹⁴ O) —, for example, by the method described in Japanese Patent Publication No. 52-4547, it is represented by the bifunctional OPE represented by the structural formula (9) and the structural formula (12). Can be introduced in an aromatic solvent such as toluene or xylene in the presence of an alkali catalyst such as potassium hydroxide, sodium ethoxide or triethylamine.

（式中、Ｑは塩素、臭素、又はヨウ素を示し、ｍは２〜６の整数を示す。）

(In the formula, Q represents chlorine, bromine, or iodine, and m represents an integer of 2 to 6.)

（式中、Ｒ¹⁴は水素原子、メチル基又はエチル基を示す。）

(In the formula, R ¹⁴ represents a hydrogen atom, a methyl group or an ethyl group.)

  In order to produce OPE-2Gly which is an intermediate of the present invention, the bifunctional OPE represented by the above structural formula (9) or structural formula (10) is used, but the powder or reaction separated from the reaction solution Either of the forms dissolved in the liquid can be used.

  Although it does not specifically limit as halogenated glycidyl used for glycidylation, Epichlorohydrin or epibromohydrin is preferable for reasons, such as availability. The amount used is preferably in the range of 1 to 100 mol, particularly 5 to 60 mol, per 1 mol of the bifunctional OPE of the structural formula (9) or the structural formula (10).

  As the base, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and the like can be used. The amount used is preferably in the range of 0.1 to 10 mol, particularly 1 to 4 mol with respect to 1 mol of the bifunctional OPE of the structural formula (9) or structural formula (10).

  The reaction temperature for carrying out the dehydrohalogenation reaction is preferably between -10 ° C and 120 ° C. After completion of the reaction, the salt produced as a by-product is removed by washing with water, and then excess glycidyl halide is distilled off under reduced pressure to obtain OPE-2Gly as a solid.

  The sulfonic acid alkali metal salt or sulfonic acid alkaline earth metal salt of the polyphenylene ether oligomer of the present invention is obtained by subjecting both end epoxy groups of OPE-2Gly obtained by the above method to an alkali (earth) metal sulfonate. Can be manufactured. As an alkali (earth) metal chlorination reagent for epoxy group, it is preferable to use a compound selected from sodium bisulfite, potassium bisulfite, sodium disulfite, and potassium disulfite. In this case, sulfonic acid for epoxy group is used. The molar ratio of sulfur element (S / epoxy group) in the alkali (earth) metal chlorinating reagent is preferably 1.0 or more, and more preferably in the range of 1.0 to 1.2.

  This production is preferably carried out in an organic solvent. Such an organic solvent is not limited as long as it can dissolve or disperse the intermediate OPE-2Gly, but the solubility of OPE-2Gly is not limited. It is preferable to use an organic polar solvent from the viewpoint of easiness of the alkali (earth) metal chlorination reaction and the dispersibility of the alkali metal (sulfonic) metal salt of the polyphenylene ether oligomer product. Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ester solvents such as ethyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, ether solvents such as dioxane, tetrahydrofuran, propylene glycol monomethyl ether, diacetone alcohol, etc. Alcohol solvents etc. Although it is shown, but is not limited thereto.

  Further, this production is preferably carried out in the presence of water in order to dissolve the above-mentioned alkali (earth) metal chlorinating reagent and enhance the reactivity. In particular, sodium disulfite and potassium disulfite are converted to alkali sulfonate ( When used as a (earth) metal chlorinating reagent, the use of water is essential in order to convert them into sodium bisulfite and potassium bisulfite. Further, in order to increase the reaction efficiency, it is optional to further use a catalytic amount of sodium sulfite, potassium sulfite or the like.

  Therefore, as an actual production formulation example, the intermediate OPE-2Gly is dissolved in an organic polar solvent, and a predetermined amount of an alkali (earth) metal chlorinating reagent and an aqueous solution of the above catalyst are dropped therein. The method of performing reaction for predetermined time is mentioned. Here, the dropping and reaction can be performed at room temperature to reflux conditions, but in order to make the reaction proceed more easily, it is preferably performed under heating conditions of 50 ° C. or higher. More preferably, the reaction is carried out under reflux conditions. The reaction time is not particularly limited, but the epoxy group can be converted to an alkali (earth) metal sulfonate by reacting for 1 to 20 hours, more preferably 2 to 8 hours under reflux conditions.

  As the reaction proceeds, the product sulfonate alkali (earth) metal salt of the polyphenylene ether oligomer is insolubilized to precipitate particles, and the reaction solution becomes suspended. After completion of the reaction, the crude product can be obtained by distilling off the water and the organic polar solvent in the reaction solution, and the crude product can be finished as it is, but the alkali sulfonate ( By removing the earth) metal chloride reagent or dissolving and removing the unreacted intermediate oligomer by washing with an organic solvent, a product with higher purity can be obtained. When used as an additive for an organic resin as in the present invention, it is preferable to remove the remaining water and organic solvent by drying under reduced pressure and pulverize them to obtain a fine powder.

  The blending amount of the sulfonic acid alkali metal salt or sulfonic acid alkaline earth metal salt of the PPE oligomer is 0.01 to 3.0 parts by mass, preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the polycarbonate resin. More preferably, it is 0.08 to 1.5 parts by mass. When the blending amount of the sulfonic acid alkali metal salt or sulfonic acid alkaline earth metal salt of the PPE oligomer is less than 0.01 parts by mass, it is difficult to obtain sufficient flame retardancy, and when it exceeds 3.0 parts by mass, thermal decomposition occurs. It becomes easy and flame retardance falls and transparency also falls.

  When the flame retardant polycarbonate resin composition of the present invention is blended with a flame retardant comprising a silicone compound, the flame retardancy may be further improved. This is thought to be because the silicone compound crosslinks during combustion to form a flame retardant layer, and various conventionally known silicone compounds can be added.

The silicone compound is not particularly limited, but it is preferable to use an organopolysiloxane having a phenyl group bonded to a silicon atom in the molecule, represented by the following average composition formula (13). .
R ¹⁵ _n R ¹⁶ _p (OR ¹⁷ ) _q (OH) _r SiO _{(4-npqr) / 2} (13)
(Wherein R ¹⁵ is a phenyl group, R ¹⁶ is a group selected from a hydrogen atom and a monovalent hydrocarbon group excluding a phenyl group having 1 to 6 carbon atoms, and R ¹⁷ is a monovalent hydrocarbon having 1 to 4 carbon atoms. N, p, q, r are 0.1 ≦ n ≦ 2.0, 0.2 ≦ p ≦ 2.5, 0 ≦ q ≦ 1.5, 0 ≦ r ≦ 0.35, 0 .9 ≦ n + p + q + r ≦ 2.8.)

This organopolysiloxane has a phenyl group bonded to a silicon atom in the molecule from the viewpoint of dispersibility in a polycarbonate resin and a flame retardant effect. From the viewpoint of imparting this characteristic, the phenyl group ( N corresponding to the number of moles of substitution of R ¹⁵ ) is preferably in the range of 0.1 ≦ n ≦ 2.0, and more preferably in the range of 0.15 ≦ n ≦ 1.4.

On the other hand, R ¹⁶ is a monovalent hydrocarbon group excluding a hydrogen atom or a phenyl group having 1 to 6 carbon atoms, and by containing an appropriate amount of this substituent, steric hindrance of an organopolysiloxane molecule containing a bulky phenyl group. This improves the degree of freedom in space, facilitates the overlap of phenyl groups and enhances the flame retarding effect, and when R ¹⁶ is a hydrogen atom, it has a reactive Si—H group. A flame retardant effect can also be expected. Accordingly, as R ¹⁶ , an alkyl group having 1 to 6 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group; An alkenyl group of 6 is preferred. In particular, a hydrogen atom, a methyl group and a vinyl group are preferred industrially from the viewpoint of alleviating steric hindrance. In order to obtain the effects as described above, it is preferable that the content of R ¹⁶ is in the range of 0.2 ≦ p ≦ 2.5 in terms of the value of p in the above formula (13), more preferably 0.8. The range is 5 ≦ p ≦ 2.1.

In addition, by containing an alkoxy group in the organopolysiloxane, the flame retardant layer is formed in the combustion part by combining the organopolysiloxane and the polycarbonate resin by oxidative degradation crosslinking of the alkoxy group during combustion, and dripping of the ignition particles (drip) ) Is prevented. R ^{17 in} the alkoxy group of the above formula (13) is a monovalent hydrocarbon group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group. Illustratively, a methyl group is particularly preferably used industrially. An alkyl group having 5 or more carbon atoms has low reactivity as an alkoxy group, and a flame retarding effect cannot be expected when an alkoxy group is introduced. On the other hand, too many alkoxy groups result in low molecular weight organopolysiloxane, which increases the loss rate due to vaporization by heat before crosslinking reaction during combustion. ) In q) is preferably 1.5 or less, more preferably 1.2 or less. The lower limit of q is more preferably 0.05 or more, particularly 0.1 or more.

  Furthermore, silanol groups contained in the organopolysiloxane may remain slightly in production, but have low reactivity and hardly contribute to flame retardancy, but are melt-processed with storage stability and polycarbonate resin. In view of stability and moldability, the content is preferably 0.35 or less, more preferably 0.3 or less, particularly preferably 0 in terms of the value of r in the above formula (13). .

  As such a phenyl group-containing organopolysiloxane, those having any composition and structure can be effectively used as long as the above conditions are satisfied. Two or more kinds of organopolysiloxanes having different compositions and structures can be used. In the present invention, an organopolysiloxane having a phenyl group bonded to a silicon atom and a methyl group and further having a branched structure in the molecule, and a phenyl group bonded to a silicon atom in the molecule. An organopolysiloxane having a monovalent hydrocarbon group such as a methyl group or a vinyl group and an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, a methyl group and a Si-H group bonded to a silicon atom in the molecule. And an organopolysiloxane having a Si-H content in the range of 0.1 to 1.2 mol / 100 g is particularly preferably used. .

In addition, the branched structure said here contains a trifunctional siloxane unit and / or a tetrafunctional siloxane unit in the structure of organopolysiloxane, and Si-H content is contained per 100 g of organopolysiloxane. This can be determined by measuring the volume of hydrogen gas generated per unit weight of the organopolysiloxane by an alkali decomposition method. For example, when 122 ml of hydrogen gas is generated per 1 g of organopolysiloxane at 25 ° C., the Si—H content is 0.5 mol / 100 g according to the following calculation formula.
122 × 273 / (273 + 25) ÷ 22400 × 100≈0.5

  Further, the molecular weight of the phenyl group-containing organopolysiloxane is not particularly limited, but if the molecular weight is too large or too small, the dispersibility to the polycarbonate resin and the flame retardant effect are insufficient, so the above In the formula (13), the range of 0.9 ≦ n + p + q + r ≦ 2.8 is preferable, and the range of 1.1 ≦ n + p + q + r ≦ 2.6 is more preferable. Furthermore, it is more preferable that the polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) is in the range of 410 to 50,000, particularly 600 to 15,000.

  Such an organopolysiloxane having a phenyl group bonded to a silicon atom in the molecule can be produced by a conventionally known method. For example, according to the structure of the desired organopolysiloxane, the corresponding organochlorosilanes may be co-hydrolyzed in the presence of alcohol having 1 to 4 carbon atoms to remove by-product hydrochloric acid and low-boiling components. You can get things. In addition, when starting from organic residues such as phenyl group, methyl group, vinyl group, alkoxysilanes having Si-H bond, silicone oil or cyclic siloxane in the molecule, hydrochloric acid, sulfuric acid, methanesulfone Using an acid catalyst such as an acid, and optionally adding water for hydrolysis to allow the polymerization reaction to proceed, and then removing the used acid catalyst and low-boiling components in the same manner to achieve the desired organo Polysiloxane can be obtained.

  In addition, when the molded product obtained by shape | molding the flame-retardant polycarbonate resin composition of this invention does not require transparency, it describes in Unexamined-Japanese-Patent No. 2003-253109 and Unexamined-Japanese-Patent No. 2003-253110. The molecule contains a methyl group and a Si—H group as a substituent bonded to a silicon atom, does not contain an aromatic hydrocarbon group, and has a Si—H content of 0.1 to 1.6 mol / 100 g. An organopolysiloxane may be added as a flame retardant.

  In the present invention, when a flame retardant comprising a silicone compound is blended, it is preferably added in a range of 0.01 to 5.0 parts by weight, more preferably 0.1 to 100 parts by weight of the polycarbonate resin. The range is 3.0 parts by mass. If the amount added is less than 0.01 parts by mass, the effect of improving dispersibility is insufficient, and if it exceeds 5.0 parts by mass, there is no further improvement in flame retardancy, which adversely affects the appearance and strength of the molded product. .

  The flame retardant polycarbonate resin composition containing the sulfonated alkali metal salt or alkaline earth metal sulfonate of the PPE oligomer is added to other thermoplastic resins, elastomers, ultraviolet absorbers, phenolic oxidations as necessary. Reinforcing agents, phosphorus heat stabilizers, pigments, dyes, lubricants, mold release agents, plasticizers, antistatic agents, slidability improving agents, glass fibers, glass flakes, carbon fibers, metal fibers, etc. Materials or inorganic fillers such as whiskers such as potassium titanate, aluminum borate and calcium silicate, mica, talc and clay can be added and blended. However, it is preferable not to mix a halogen-based flame retardant and a phosphorus-based flame retardant. These addition methods can be appropriately added by a conventionally known method utilizing these characteristics.

  As a method of mixing the sulfonic acid alkali metal salt or sulfonic acid alkaline earth metal salt of the PPE oligomer and the polycarbonate resin, various kneaders such as uniaxial and multiaxial kneaders, Banbury mixers, rolls, Brabender plastograms, etc. The above components are kneaded and then cooled and solidified, or the above components are added to a suitable solvent, for example, hydrocarbons such as hexane, heptane, benzene, toluene, xylene and their derivatives, and the components to be dissolved or dissolved. A solution mixing method or the like in which components and insoluble components are mixed in a suspended state is used. The melt-kneading method is preferable from the industrial cost, but is not limited thereto. In the melt-kneading, it is preferable to use a uniaxial or biaxial extruder.

  The method for obtaining a molded product from the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, and is a molding method generally used for thermoplastic resin compositions, for example, injection molding, hollow molding, extrusion molding. A molding method such as sheet molding, thermoforming, rotational molding, and lamination molding can be applied.

  The present invention will be described more specifically with reference to the following examples. However, the examples are only intended to illustrate the present invention. The present invention is not limited by the following examples unless it exceeds the gist. In the examples and comparative examples, the following raw materials were used.

[raw materials]
(1) Polycarbonate resin: poly-4,4-isopropylidene diphenyl carbonate, trade name: Iupilon (registered trademark) S-3000 (viscosity average molecular weight 21,500), manufactured by Mitsubishi Engineering Plastics (hereinafter "PC resin") Abbreviated).
(2) PPE oligomer sulfonic acid sodium salt: According to the following synthesis example (hereinafter abbreviated as “OPE-Na”).
(3) PPE oligomer sulfonate potassium salt: According to the following synthesis example (hereinafter abbreviated as “OPE-K”).
(4) Phosphorus flame retardant: Triphenyl phosphate, manufactured by Daihachi Chemical Co., Ltd. (hereinafter abbreviated as “TPP”).
(5) Phenol-based antioxidant: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], trade name: IRGANOX 1010, manufactured by Ciba Specialty Chemicals Co., Ltd. Abbreviated as “antioxidant”).
(6) Thermal stabilizer: Tris (2,4-di-tert-butylphenyl) phosphite, trade name: ADK STAB 2112, manufactured by Asahi Denka Kogyo Co., Ltd. (hereinafter abbreviated as “thermal stabilizer”).

Moreover, the identification and analysis of the compound obtained by the synthesis example were implemented by the method shown below.
(I) The structure of bifunctional OPE and OPE-2Gly was identified by ¹ H-NMR, ¹³ C-NMR, and IR analysis.
(II) The number average molecular weight and weight average molecular weight of the bifunctional OPE and OPE-2Gly were determined by gel permeation chromatography (hereinafter referred to as GPC) method. Data processing was performed from the GPC curve and molecular weight calibration curve of the sample. The molecular weight calibration curve was obtained by approximating the relationship between the molecular weight of standard polystyrene and the elution time to the following equation.
LogM = A ₀ X ³ + A ₁ X ² + A ₂ X + A ₃ + A ₄ / X ²
(Here, M: molecular weight, X: elution time -19 (min), A _{0 to} A ₄ : coefficient)
(III) The hydroxyl equivalent of bifunctional OPE is 2,600 dimethylphenol as a standard substance, dissolved in dry dichloromethane and subjected to IR analysis (liquid cell method; cell length = 1 mm), absorption of 3,600 cm ⁻¹ Obtained from strength.
(IV) The peak of phenolic hydroxyl group (3,600 cm ⁻¹ ) of bifunctional OPE used as a raw material has disappeared from OPE-2Gly by IR analysis, and the phenolic hydroxyl group is glycidylated. It was confirmed.
(V) The sulfonic acid alkali metal salt of the polyphenylene ether oligomer obtained in the examples was decomposed with nitric acid, and then subjected to ICP-AES, and the contents of S element and Na element or K element were determined by absolute calibration method. It was measured.

[Synthesis Example 1] Synthesis of bifunctional OPE 13 g of copper (I) chloride, 795 g of di-n-butylamine, 6,000 g of toluene in a 20-liter vertical reactor equipped with a stirrer, thermometer, air introduction tube and baffle plate 2,2 ′, 3,3 ′, 5,5′-hexamethyl- (1,1′-biphenyl) -4 previously dissolved in 6,000 g of methanol. , 4′-diol 418 g and 2,6-dimethylphenol 915 g mixed solution (molar ratio of divalent phenol to monovalent phenol = 1: 5) while bubbling air at 2 L / min for 150 minutes The mixture was stirred while dropping. Ethylenediaminetetraacetic acid dihydrogen disodium aqueous solution was added to this, and reaction was stopped. Then, it was washed with 1N hydrochloric acid aqueous solution and then with ion exchange water. The obtained solution was concentrated by an evaporator to obtain 2,560 g of a 50 mass% toluene solution of bifunctional OPE. As a result of measuring the obtained bifunctional OPE by GPC method, it was number average molecular weight = 980 and weight average molecular weight = 1,510. Further, the hydroxyl equivalent weight was 490 g / mol.

[Synthesis Example 2] Synthesis of OPE-2Gly A reactor having a capacity of 5 L equipped with a stirrer, a thermometer, and a dropping funnel was heated to 100 ° C., and 800 g of a 50 mass% toluene solution of the bifunctional OPE obtained above and epi 2,100 g of chlorohydrin was charged. Thereafter, 201 g of a 23 mass% ethanol solution of sodium ethoxide was added dropwise from the dropping funnel over 1 hour, and stirring was further performed for 5 hours after completion of the addition. The reaction mixture was washed with ion exchange water, and then the organic layer was separated. Toluene and excess epichlorohydrin were distilled off from the resulting solution, followed by drying under reduced pressure to obtain 430 g of OPE-2Gly. The obtained OPE-2Gly was measured by the GPC method. As a result, the number average molecular weight was 1,040 and the weight average molecular weight was 1,650. Moreover, it was epoxy equivalent = 515g / mol.

Synthesis Example 3 Synthesis of OPE-Na A 1 L flask equipped with a stirrer, a cooling condenser, a thermometer, and a dropping funnel was charged with 206 g of OPE-2Gly obtained above and 481 g of methyl isobutyl ketone, and 1 at room temperature. It stirred for time and melt | dissolved and it was set as the homogeneous solution. While maintaining the inner temperature of 80 to 90 ° C. by heating the inside of the flask, an aqueous solution consisting of 43.7 g of sodium bisulfite, 2.5 g of sodium sulfite and 115.5 g of ion-exchanged water was added dropwise over 1 hour, followed by reflux conditions. The reaction was stirred for 5 hours below.

  This was heated in an oil bath at 130 ° C. to substantially distill off water and methyl isobutyl ketone, then cooled to room temperature, added again with 400 g of methyl isobutyl ketone, and stirred at room temperature for 1 hour to uniformly disperse. The solution was then filtered to remove unreacted OPE-2Gly dissolved in methyl isobutyl ketone. Further, cake-like undissolved methyl isobutyl ketone was washed with acetone, then added to 500 g of ion-exchanged water, stirred at room temperature for 1 hour to obtain a uniform dispersion, and then filtered, and the remaining sodium hydrogen sulfite and sulfurous acid. Sodium was removed as an aqueous solution. The obtained cake was washed with acetone, dried under reduced pressure at 80 ° C. for 6 hours under reduced pressure of 10 mmHg to remove residual acetone and moisture, and then pulverized in a mortar to obtain 210 g of a fine yellowish white powder. .

The OPE-Na thus obtained is obtained by replacing R ² , R ³ , R ⁴ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ with a methyl group in the structural formulas (1) to (4). , R ⁵ , R ⁶ , R ¹² , R ¹³ are hydrogen atoms, and M is sodium, a + b = 6, c = 0, d = 0, and this is obtained by nitric acid decomposition / ICP-AES method As a result of the analysis, the S element content = 4.9% by mass (theoretical value = 5.2% by mass) and the Na element content = 3.6% by mass (theoretical value = 3.7% by mass).

[Synthesis Example 4] Synthesis of OPE-K A 1 L flask equipped with a stirrer, a cooling condenser, a thermometer, and a dropping funnel was charged with 204 g of OPE-2Gly obtained above and 476 g of propylene glycol monomethyl ether at 80 ° C. The mixture was dissolved by stirring for 1 hour to obtain a uniform solution. While maintaining the inner temperature of 80 to 90 ° C. by heating the inside of the flask, an aqueous solution consisting of 46.7 g of potassium disulfite, 3.2 g of potassium sulfite and 138 g of ion-exchanged water was added dropwise over 1 hour, and then continuously under reflux conditions. The reaction was stirred for 5 hours.

  This was heated in an oil bath at 140 ° C. to substantially distill off water and propylene glycol monomethyl ether, then cooled to room temperature, 400 g of propylene glycol monomethyl ether was added again, and the mixture was stirred at 60 ° C. for 1 hour. Filtration was performed after preparing a uniform dispersion, and unreacted OPE-2Gly dissolved in propylene glycol monomethyl ether was removed. Further, the cake-like propylene glycol monomethyl ether undissolved material was washed with acetone, added to 600 g of ion-exchanged water, stirred at room temperature for 1 hour to obtain a uniform dispersion, filtered, and the remaining potassium disulfite and Potassium sulfite was removed as an aqueous solution. The obtained cake was washed with acetone, dried under reduced pressure at 80 ° C. for 6 hours under reduced pressure of 10 mmHg to remove residual acetone and moisture, and then pulverized in a mortar to obtain 216 g of a pale yellow fine powder. .

The OPE-K thus obtained is obtained by replacing R ² , R ³ , R ⁴ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ with a methyl group in the structural formulas (1) to (4). , R ⁵ , R ⁶ , R ¹² , and R ¹³ are hydrogen atoms, and M is potassium, a + b = 6, c = 0, d = 0, and this is obtained by nitric acid decomposition / ICP-AES method As a result of analysis, the S element content was 4.7% by mass (theoretical value = 5.1% by mass), and the K element content was 5.8% by mass (theoretical value = 6.2% by mass).

[Synthesis Example 5] Synthesis of Organopolysiloxane B-1 According to the method described in Preparation Example 1 of Japanese Patent Application Laid-Open No. 2003-253109, a 1-L flask equipped with a stirrer, a cooling device, and a thermometer was added to 91.9 g of siloxane and 408.1 g of 1,3,5,7-tetramethylcyclotetrasiloxane were charged, and 15.0 g of concentrated sulfuric acid was added while further stirring. After completion of the addition, stirring was further continued for 5 hours at an internal temperature of 20 to 25 ° C., and then 6.4 g of water was added, stirred for 1 hour, and allowed to stand to remove the separated aqueous layer. Thereafter, it was further washed four times with a 5% sodium sulfate aqueous solution to confirm that the siloxane layer became neutral. The siloxane layer was heated to an internal temperature of 120 ° C. under reduced pressure to remove the low boiling point, and then insolubles were removed by filtration to obtain organopolysiloxane B-1. This organopolysiloxane B-1 contains only a methyl group and a Si—H group as a substituent bonded to a silicon atom in the molecule, has the following structure, and has a Si—H group content of 1. It was 38 mol / 100 g and the weight average molecular weight was 950.

[Synthesis Example 6] Synthesis of Organopolysiloxane B-2 In accordance with the method described in Preparation Example 4 of JP-A-2003-253109, a 1 L flask equipped with a stirrer, a cooling device, and a thermometer was charged with water 537. 6 g and 120 g of toluene were charged and cooled to an internal temperature of 5 ° C. A mixture of 12.6 g of trimethylchlorosilane, 120.1 g of methyldichlorosilane, and 36.7 g of diphenyldichlorosilane was charged into the dropping funnel and dropped into the flask over 2 hours while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged for 4 hours with stirring at an internal temperature of 20 ° C., and the hydrochloric acid aqueous layer separated by standing was removed. To this was added 80 g of a 10% aqueous sodium carbonate solution, stirred for 5 minutes, and then allowed to stand to remove the separated aqueous layer. Then, it wash | cleaned 3 times with ion-exchange water, and it confirmed that the toluene layer became neutral. This toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling components, and then insolubles were removed by filtration to obtain organopolysiloxane B-2. This organopolysiloxane B-2 contains a methyl group, a Si—H group and a phenyl group as substituents for bonding to a silicon atom in the molecule, has the following structure, and has a Si—H group content. 1.07 mol / 100g and the weight average molecular weight were 3,600.

[Synthesis Example 7] Synthesis of Organopolysiloxane B-3 According to the method described in Preparation Example 1 of JP-A-2003-253110, 288 g of water and toluene were added to a 1 L flask equipped with a stirrer, a cooling device, and a thermometer. 93 g was charged and heated to an internal temperature of 80 ° C. in an oil bath. A dropping funnel was charged with 148 g of phenyltrichlorosilane, 51 g of diphenyldichlorosilane, and 13 g of dimethyldichlorosilane, and was dropped into the flask over 1 hour while stirring. After completion of the dropping, the mixture was further aged at an internal temperature of 80 ° C. for 1 hour. . Subsequently, 27 g of trimethylchlorosilane was dropped into the flask over 10 minutes while stirring, and after completion of the dropping, stirring was further continued for 30 minutes at an internal temperature of 80 ° C. for aging. 100 g of toluene was added, and the aqueous layer that had been separated by leaving to stand while cooling to room temperature was removed. Subsequently, a 10% aqueous sodium sulfate solution was mixed, stirred for 10 minutes, and then left to stand for 30 minutes, and the separated aqueous layer The reaction was stopped by repeating the water washing operation to remove water until the toluene layer became neutral. An ester adapter was attached, and the toluene layer containing the organopolysiloxane was heated to reflux to remove water from the toluene layer. After the internal temperature reached 110 ° C., the reaction was continued for another 1 hour, and then cooled to room temperature. The obtained organopolysiloxane solution was filtered to remove insoluble matters, and then toluene and low-molecular siloxane were removed by distillation under reduced pressure to obtain a solid phenyl group-containing organopolysiloxane B-3. This phenyl group-containing organopolysiloxane B-3 contains a phenyl group and a methyl group as substituents for bonding to a silicon atom in the molecule, and further has a branched structure, and this has an average composition formula R ¹ _m R ² _n (OR ³ ) _p (OH) _q SiO _{(4-mnpq) / 2} , R ² = methyl group, m = 0.93, n = 0.62, p = 0, q = 0.03, m + n + p + q = 1.58, the weight average molecular weight was 9,200, and the softening point was 96 ° C.
(Ph) _0.93 (Me) _0.62 (OH) _0.03 SiO _{2.42 / 2}

  The Si-H group content in each organopolysiloxane obtained in Synthesis Examples 5 to 7 is to measure the volume of hydrogen gas generated per unit weight of the organopolysiloxane by the alkali decomposition method as described above. The weight average molecular weight is a numerical value converted from a GPC (gel permeation chromatography) measurement data using a calibration curve prepared with a polystyrene standard sample.

[Examples 1-7, Comparative Examples 1-4]
Each component was mix | blended with the mixing | blending prescription shown in Table 1 and Table 2, and it knead | mixed and pelletized with the barrel temperature of 260 degreeC with the single screw extruder VS-40 (made by Tanabe Plastics). The obtained pellets were dried at 120 ° C. for 5 hours, and then used under the conditions of cylinder temperature: 270 ° C. and mold temperature: 100 ° C. using Psycap M-2, mold clamping force 75T manufactured by Sumitomo Heavy Industries, Ltd. Various test pieces were injection-molded in a cycle of 60 seconds, and the obtained test pieces were used for evaluation by the following methods. The results are shown in Tables 1 and 2. By comparing Table 1 and Table 2, the flame-retardant polycarbonate resin composition of the present invention has an Izod impact strength, total light transmittance (transparency), flame retardancy, and residence heat stability (small ΔYI). It became clear that it was excellent.

[Evaluation of specimen]
(1) Izod impact strength: According to ASTM D256.
(2) Light transmittance: A plate of 80 mm × 40 mm × 3.2 mmt was molded, and the total light transmittance was measured according to ASTM D1003.
(3) Flammability: A 3.0 mm thick flammability test was conducted according to the UL94 vertical flammability test.
(4) Degree of yellowing: After drying the pellets at 120 ° C. for 5 hours, cylinder temperature: 300 ° C., mold temperature: 100, using Sumitomo Heavy Industries, Ltd., Psycap M-2, mold clamping force 75T An 80 mm × 40 mm × 3.2 mmt plate was injection-molded (retention molding) in a cycle of 3 minutes under the condition of ° C., and the hue (YI) was measured with a color difference meter SM-3-CH manufactured by Suga Test Instruments Co., Ltd. . At the same time, the hue (YI) of the plate obtained by the above molding (2) (normal molding) was measured. The difference in hue between the normal molding plate and the retention molding plate is defined as the yellowing degree (ΔYI), and the smaller the yellowing degree (ΔYI), the better the retention thermal stability.

Claims (5)

0.01 to 3.0 parts by mass of an alkali metal sulfonate or alkaline earth metal sulfonate of a polyphenylene ether oligomer represented by the following structural formula (1) with respect to 100 parts by mass of the polycarbonate resin. A flame retardant polycarbonate resin composition characterized by the above.

(In the formula, — (O—X—O) — is represented by the structural formula (2), and R ² , R ³ , R ⁴ , R ⁸ and R ⁹ may be the same or different, and may be a halogen atom, R ⁵ , R ⁶ , and R ⁷ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. (Y-O) - is one in which one kind of structure defined, or two or more kinds of structures defined by the formula (3) are arranged in a random structure (3) .R ^10, R ¹¹ may be the same or different, and is a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R ¹² and R ¹³ may be the same or different, and are a hydrogen atom, a halogen atom, or 6 or less carbon atoms. Z is a divalent organic group having 1 to 6 carbon atoms, and is an oxygen atom. Although may contain a .R ¹ are those having a group represented by the structural formula (4) mandatory, part of R ¹ may be hydrogen atom or a glycidyl group, M is an alkali metal and (It is an alkaline earth metal. A and b represent an integer of 0 to 100. c and d represent an integer of 0 to 20.)

-(O—X—O) — of the sulfonic acid alkali metal salt or sulfonic acid alkaline earth metal salt of the polyphenylene ether oligomer represented by the formula (1) is represented by the structural formula (5), and — (Y—O 2. The flame retardant polycarbonate resin composition according to claim 1, wherein the structural formula (6) or the structural formula (7) or the structural formula (6) and the structural formula (7) are randomly arranged. object.

  The M in the structural formula (4) of the alkali metal sulfonate or alkaline earth metal sulfonate of the polyphenylene ether oligomer represented by the formula (1) is sodium and / or potassium. Or the flame-retardant polycarbonate resin composition of 2.   Furthermore, 0.01-5.0 mass parts of flame retardants which consist of a silicone type compound are mix | blended with respect to 100 mass parts of polycarbonate resin, The any one of Claims 1 thru | or 3 characterized by the above-mentioned. Flame retardant polycarbonate resin composition. A molded article obtained by molding the flame-retardant polycarbonate resin composition according to any one of claims 1 to 4.