JP2009249621A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition containing a large amount of portion derived from a biological-originated substance, excellent in both heat resistance and thermal stability, excellent in rigidity and flame retardancy, and useful as an industrial material having excellent molding workability. <P>SOLUTION: This flame-retardant polycarbonate resin contains 20-200 pts.wt. of metal hydroxide (B component) per 100 pts.wt. of polycarbonate resin (A component) containing carbonate constitutive units expressed by formula (1). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel flame-retardant polycarbonate resin composition. More specifically, a resin comprising a polycarbonate resin and a specific flame retardant containing a portion that can be derived from a carbohydrate that is a biogenic substance, having both good heat resistance and thermal stability, and having rigidity and flame retardancy. The present invention relates to a flame retardant polycarbonate resin composition which is a composition and is useful as a raw material for various molding materials and polymer alloy materials.

  The polycarbonate resin is a polymer in which an aromatic or aliphatic dioxy compound is linked by a carbonic acid ester, and among them, a polycarbonate resin obtained from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) (hereinafter “PC-”). A ”(sometimes referred to as“ A ”) is excellent in transparency and heat resistance, and has excellent mechanical properties such as impact resistance and is used in many fields.

  Polycarbonate resins are generally produced using raw materials obtained from petroleum resources. However, there is a concern about the exhaustion of petroleum resources, and there is a demand for production of polycarbonate resins using raw materials obtained from biological materials such as plants. ing.

  A typical example of a biomass material that uses biogenic materials as raw materials is polylactic acid. Among biomass plastics, it has relatively high heat resistance and mechanical properties, so its application is expanding to tableware, packaging materials, general merchandise, etc. However, the possibility as an industrial material has been studied. However, polylactic acid has insufficient heat resistance when used as an industrial material, and when it is attempted to obtain a molded product by injection molding with high productivity, the crystalline polymer is low in crystallinity, so that the moldability is low. Is inferior. From this point of view, considering the development of biomass materials into industrial materials, there is a demand for amorphous biomass materials such as polycarbonate resins.

  As a polycarbonate resin using a biogenic material as a raw material, a polycarbonate resin using a raw material obtained from an ether diol residue that can be produced from a saccharide in addition to a polylactic acid resin has been studied.

に示したエーテルジオールは、たとえば糖類およびでんぷんなどから容易に作られ、３種の立体異性体が知られているが、具体的には下記式（ｂ）

に示す、１，４：３，６−ジアンヒドロ−Ｄ−ソルビトール（本明細書では以下「イソソルビド」と呼称する）、下記式（ｃ）

に示す、１，４：３，６−ジアンヒドロ−Ｄ−マンニトール（本明細書では以下「イソマンニド」と呼称する）、下記式（ｄ）

に示す、１，４：３，６−ジアンヒドロ−Ｌ−イジトール（本明細書では以下「イソイディッド」と呼称する）である。 For example, the following formula (a)

The ether diol shown in Fig. 2 is easily made from, for example, sugars and starch, and three stereoisomers are known. Specifically, the following formula (b)

1,4: 3,6-dianhydro-D-sorbitol (hereinafter referred to as “isosorbide”), represented by the following formula (c)

1,4: 3,6-dianhydro-D-mannitol (hereinafter referred to as “isomannide”), represented by the following formula (d):

1,4: 3,6-dianhydro-L-iditol (hereinafter referred to as “isoidid”).

  Isosorbide, isomannide, and isoidide are obtained from D-glucose, D-mannose, and L-idose, respectively. For example, isosorbide can be obtained by hydrogenating D-glucose and then dehydrating it using an acid catalyst.

  So far, among the above-mentioned ether diols, in particular, incorporation into polycarbonate using isosorbide as a monomer has been studied. Among them, isosorbide homopolycarbonate is described in Patent Documents 1 and 2 and Non-Patent Documents 1 and 2.

  Of these, Patent Document 1 reports a homopolycarbonate resin having a melting point of 203 ° C. using a melt transesterification method. However, this polymer has insufficient mechanical properties. In Non-Patent Document 1, a homopolycarbonate resin having a glass transition temperature of 166 ° C. is obtained in a melt transesterification method using zinc acetate as a catalyst, but a thermal decomposition temperature (5% weight loss temperature) is 283 ° C. Stability is not enough. In Non-Patent Document 2, homopolycarbonate resin is obtained by interfacial polymerization using bischloroformate of isosorbide, but the glass transition temperature is 144 ° C. and the heat resistance is not sufficient. On the other hand, as an example of high heat resistance, Patent Document 2 reports a polycarbonate having a glass transition temperature of 170 ° C. or higher by differential calorimetry at a heating rate of 10 ° C./min. There is a problem that the melt viscosity when considered is too high. Further, this polycarbonate is produced in the presence of a tin catalyst, has a thermal decomposition temperature (5% weight loss temperature) of around 300 ° C., and there is room for improvement in thermal stability. On the other hand, Patent Document 3 describes a copolymerized polycarbonate of isosorbide and a linear aliphatic diol.

  Considering the development of these polycarbonates composed of isosorbide into industrial applications, the required characteristics vary depending on the application, but flame retardancy is industrial materials, especially electrical / electronic parts, OA related This is one of the physical properties particularly required for parts or automobile parts. However, none of these documents mentions flame retardancy.

  About the homopolycarbonate resin which consists of isosorbide, the flame-retardant level of UL-94 specification in the molded article of thickness 1.6mm is not-V. Considering the flame retardancy of polycarbonate resin composed of isosorbide, it is different from the combustion mechanism such as intramolecular transition and isomerization proposed in the known bisphenol A type aromatic polycarbonate resin to form a carbonized film. . Also, from the viewpoint of the difference in compatibility between the polycarbonate resin and the flame retardant, not all flame retardants used in the conventionally known bisphenol A type polycarbonate resin can be used as they are, and a separate study is required. In addition, from the viewpoint of safety and environmental harmony, flame retardants are being replaced with non-halogen and non-phosphorous flame retardants.

British Patent Application No. 1079686 International Publication No. 2007/013463 Pamphlet International Publication No. 2004/111106 Pamphlet “Journal of Applied Polymer Science”, 2002, 86, p. 872-880. “Macromolecules”, 1996, Vol. 29, p. 8077-8082

  The present invention solves the above-mentioned problems, contains many parts that can be derived from biological materials, has both good heat resistance and thermal stability, good rigidity and flame retardancy, and excellent molding processing An object of the present invention is to provide a flame retardant polycarbonate resin composition useful as an industrial material having properties.

で表されるカーボネート構成単位を含むポリカーボネート樹脂に、特定の金属水酸化物を含有してなる難燃性ポリカーボネート樹脂組成物が、上記目的を達成することを見出し本発明に至った。 As a result of intensive studies to achieve the above object, the present inventor has found that the following formula (1)

The present inventors have found that a flame retardant polycarbonate resin composition comprising a polycarbonate resin containing a carbonate structural unit represented by formula (I) containing a specific metal hydroxide achieves the above object.

２．ポリカーボネート樹脂（Ａ成分）は、ガラス転移温度（Ｔｇ）が１４５℃〜１６５℃であり、かつ５％重量減少温度（Ｔｄ）が３２０℃〜４００℃である前項１記載の難燃性ポリカーボネート樹脂組成物、
３．上記式（１）で表されるカーボネート構成単位がイソソルビド（１，４：３，６ージアンヒドローＤーソルビトール）由来のカーボネート構成単位である前項１または２記載の難燃性ポリカーボネート樹脂組成物、
４．金属水酸化物（Ｂ成分）が水酸化マグネシウム、および水酸化アルミニウムからなる群より選ばれる少なくとも１種の化合物である前項１〜３のいずれか１項に記載の難燃性ポリカーボネート樹脂組成物、
５．ポリカーボネート樹脂（Ａ成分）１００重量部に対して、さらにフェノール系炭化剤（Ｃ成分）５〜３０重量部を含有する前項１〜４のいずれか１項に記載の難燃性ポリカーボネート樹脂組成物、
６．ポリカーボネート樹脂（Ａ成分）１００重量部に対して、金属水酸化物（Ｂ成分）２０〜１５０重量部を含有する前項１〜５のいずれか１項に記載の難燃性ポリカーボネート樹脂組成物、
７．厚み１．６ｍｍの成形品において、ＵＬ−９４規格の難燃レベルがＶ−２を達成する前項１〜６のいずれか１項に記載の難燃性ポリカーボネート樹脂組成物、および
８．前項１〜７のいずれか１項に記載の難燃性ポリカーボネート樹脂組成物から形成された成形品、
が提供される。 That is, according to the present invention,
1. Flame-retardant polycarbonate resin containing 20 to 200 parts by weight of metal hydroxide (component B) with respect to 100 parts by weight of polycarbonate resin (component A) containing a carbonate constituent unit represented by the following formula (1) Composition,

2. The flame retardant polycarbonate resin composition according to item 1 above, wherein the polycarbonate resin (component A) has a glass transition temperature (Tg) of 145 ° C. to 165 ° C. and a 5% weight loss temperature (Td) of 320 ° C. to 400 ° C. object,
3. The flame retardant polycarbonate resin composition according to item 1 or 2, wherein the carbonate constituent unit represented by the formula (1) is a carbonate constituent unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol),
4). The flame-retardant polycarbonate resin composition according to any one of items 1 to 3, wherein the metal hydroxide (component B) is at least one compound selected from the group consisting of magnesium hydroxide and aluminum hydroxide,
5. The flame-retardant polycarbonate resin composition according to any one of the preceding items 1 to 4, further comprising 5 to 30 parts by weight of a phenol-based carbonizer (component C) with respect to 100 parts by weight of the polycarbonate resin (component A),
6). The flame-retardant polycarbonate resin composition according to any one of the preceding items 1 to 5, which contains 20 to 150 parts by weight of a metal hydroxide (component B) with respect to 100 parts by weight of the polycarbonate resin (component A),
7). 7. The flame-retardant polycarbonate resin composition according to any one of items 1 to 6, wherein the flame-retardant level of UL-94 standard achieves V-2 in a molded product having a thickness of 1.6 mm; A molded article formed from the flame retardant polycarbonate resin composition according to any one of items 1 to 7,
Is provided.

Hereinafter, the present invention will be described in detail.
The polycarbonate resin (component A) used in the present invention is a polycarbonate resin containing a carbonate constituent unit represented by the formula (1), and the constituent unit represented by the formula (1) is 60 mol in all carbonate constituent units. % Or more is preferable, 70 mol% or more is more preferable, 80 mol% or more is further preferable, and 90 mol% or more is particularly preferable. Most preferably, it is a homopolycarbonate resin consisting only of the carbonate structural unit of the formula (1).

The polycarbonate resin (component A) has a melt viscosity measured with a capillary rheometer at 250 ° C. in the range of 0.1 × 10 ^{3 to} 2.4 × 10 ³ Pa · s under conditions of a shear rate of 600 sec ^−1. It is more preferable that it is in a range of 0.2 × 10 ^{3 to} 2.0 × 10 ³ Pa · s, and a range of 0.2 × 10 ^{3 to} 1.5 × 10 ³ Pa · s is more preferable. . When the melt viscosity is within this range, the mechanical strength is excellent, and when molding using the polycarbonate resin composition of the present invention, silver is not generated during molding, which is good. Moreover, as for this polycarbonate resin (A component), the minimum of the specific viscosity in 20 degreeC of the solution which melt | dissolved 0.7 g of resin in 100 ml of methylene chlorides has preferable 0.14 or more, More preferably, it is 0.20 or more. The upper limit is preferably 0.45 or less, more preferably 0.37 or less, and still more preferably 0.34 or less. When the specific viscosity is lower than 0.14, it becomes difficult to give sufficient mechanical strength to the molded product obtained from the polycarbonate resin composition of the present invention. On the other hand, when the specific viscosity is higher than 0.45, the melt fluidity becomes too high, and the melting temperature having the fluidity necessary for molding becomes higher than the decomposition temperature.

  The lower limit of the glass transition temperature (Tg) of the polycarbonate resin (component A) used in the present invention is preferably 145 ° C or higher, more preferably 148 ° C or higher, and the upper limit is preferably 165 ° C or lower. When the Tg is less than 145 ° C., the heat resistance (particularly heat resistance due to moisture absorption) is poor, and when it exceeds 165 ° C., the melt fluidity during molding using the polycarbonate resin composition of the present invention is poor. Tg is measured by DSC (model DSC2910) manufactured by TA Instruments.

  The lower limit of the 5% weight loss temperature of the polycarbonate resin (component A) used in the present invention is preferably 320 ° C. or higher, more preferably 330 ° C. or higher, and the upper limit is preferably 400 ° C. or lower, more preferably. It is 390 degrees C or less, More preferably, it is 380 degrees C or less. It is preferable that the 5% weight loss temperature is in the above range since there is almost no decomposition of the resin when molding using the polycarbonate resin composition of the present invention. The 5% weight loss temperature is measured by TA Instruments TGA (model TGA2950).

で表されるエーテルジオールおよび炭酸ジエステルとから溶融重合法により製造することができる。エーテルジオールとしては、具体的には下記式（ｂ）、（ｃ）および（ｄ）

で表されるイソソルビド、イソマンニド、イソイディッドなどが挙げられる。 The polycarbonate resin (component A) used in the present invention has the following formula (a):

It can manufacture with the melt polymerization method from the ether diol and carbonic acid diester represented by these. As the ether diol, specifically, the following formulas (b), (c) and (d)

And isosorbide, isomannide, and isoidide represented by the formula:

  These saccharide-derived ether diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials.

  In particular, a polycarbonate resin in which the carbonate structural unit includes a carbonate structural unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol) is preferable. Isosorbide is an ether diol that can be easily made from starch, and can be obtained in abundant resources, and is superior in all ease of manufacture, properties, and versatility of use compared to isomannide and isoidide. .

  The polycarbonate resin (component A) used in the present invention may be copolymerized with aliphatic diols or aromatic bisphenols as long as the properties are not impaired. As the aliphatic diol, an aliphatic diol represented by the following formula (2) is preferably used.

（式中、ｍは１〜１０の整数）

(Where m is an integer from 1 to 10)

  Specifically, linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, etc. Among these, 1,3-propanediol, 1,4-butanediol, hexanediol, and cyclohexanedimethanol are preferable.

  As aromatic bisphenols, 2,2-bis (4-hydroxyphenyl) propane (commonly known as “bisphenol A”), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4 '-(m-phenylenediisopropylidene) diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) decane, 1,3-bis {2- (4 -Hydroxyphenyl) propyl} benzene and the like.

  In addition to the ether diol represented by the above formula (1), the aliphatic diol represented by the above formula (2) and the aromatic bisphenol, other diol residues can also be contained. Other diols include aromatic diols such as dimethanolbenzene and diethanolbenzene.

で表されるヒドロキシ化合物が好ましく用いられる。 Moreover, the polycarbonate resin (A component) used for this invention can also introduce | transduce an end group in the range which does not impair the characteristic. Such end groups can be introduced by adding the corresponding hydroxy compound during polymerization. As a hydroxy compound, following formula (3) or (4)

A hydroxy compound represented by the formula is preferably used.

であり、好ましくは炭素原子数４〜２０のアルキル基、炭素原子数４〜２０のパーフルオロアルキル基、または上記式（５）であり、特に炭素原子数８〜２０のアルキル基、または上記式（５）が好ましい。Ｙは単結合、エーテル結合、チオエーテル結合、エステル結合、アミノ結合およびアミド結合からなる群より選ばれる少なくとも一種の結合が好ましいが、より好ましくは単結合、エーテル結合およびエステル結合からなる群より選ばれる少なくとも一種の結合であり、なかでも単結合、エステル結合が好ましい。ａは１〜５の整数であり、好ましくは１〜３の整数であり、特に１が好ましい。 In the above formulas (3) and (4), R ⁴ represents an alkyl group having 4 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a perfluoroalkyl group having 4 to 30 carbon atoms, or the following formula ( 5)

Preferably an alkyl group having 4 to 20 carbon atoms, a perfluoroalkyl group having 4 to 20 carbon atoms, or the above formula (5), particularly an alkyl group having 8 to 20 carbon atoms, or the above formula. (5) is preferred. Y is preferably at least one bond selected from the group consisting of a single bond, ether bond, thioether bond, ester bond, amino bond and amide bond, more preferably selected from the group consisting of a single bond, ether bond and ester bond. It is at least one kind of bond, and among them, a single bond and an ester bond are preferable. a is an integer of 1 to 5, preferably an integer of 1 to 3, and 1 is particularly preferable.

In the above formula (5), R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, It is at least one group selected from the group consisting of an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, preferably each independently a carbon atom. And at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, particularly at least one group independently selected from the group consisting of a methyl group and a phenyl group. Is preferred. b is an integer of 0 to 3, an integer of 1 to 3 is preferable, and an integer of 2 to 3 is particularly preferable. c is an integer of 4 to 100, preferably an integer of 4 to 50, and particularly preferably an integer of 8 to 50.

  Since the polycarbonate resin (component A) used in the present invention has a carbonate structural unit in the main chain structure using raw materials obtained from renewable resources such as plants, these hydroxy compounds are also derived from renewable resources such as plants. The obtained raw material is preferable. Examples of hydroxy compounds obtained from plants include long-chain alkyl alcohols having 14 or more carbon atoms (cetanol, stearyl alcohol, behenyl alcohol) obtained from vegetable oils.

  The polycarbonate resin (component A) used in the present invention is a mixture of a bishydroxy compound containing an ether diol represented by the formula (a) and a carbonic acid diester, and the alcohol or phenol produced by the transesterification reaction is decompressed at high temperature. It can be obtained by carrying out a melt polymerization which is distilled under.

  The reaction temperature is preferably as low as possible in order to suppress decomposition of the ether diol and obtain a highly viscous resin with little coloration, but the polymerization temperature is 180 ° C. to 280 ° C. in order to proceed the polymerization reaction appropriately. It is preferably in the range of ° C, more preferably in the range of 180 ° C to 270 ° C.

In the initial stage of the reaction, ether diol and carbonic acid diester are heated at normal pressure and pre-reacted, and then gradually reduced in pressure, and the system is changed to 1.3 × 10 ^{−3 to} 1.3 × 10 ^{− in the} late stage of the reaction. A method of facilitating the distillation of alcohol or phenol produced by reducing the pressure to about ⁵ MPa is preferred. The reaction time is usually about 1 to 4 hours.

  A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, alkali metal compounds such as sodium salt or potassium salt of dihydric phenol, calcium hydroxide, barium hydroxide, magnesium hydroxide. And alkaline earth metal compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, nitrogen-containing basic compounds such as trimethylamine and triethylamine. These may be used alone or in combination of two or more. Among these, it is preferable to use a nitrogen-containing basic compound and an alkali metal compound in combination.

The amount of these polymerization catalysts used is preferably in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻³ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁴ equivalents, relative to 1 mol of the carbonic acid diester component. Chosen by The reaction system is preferably maintained in an atmosphere of a gas inert to the raw materials such as nitrogen, the reaction mixture, and the reaction product. Examples of inert gases other than nitrogen include argon. Furthermore, you may add additives, such as antioxidant, as needed.

  Examples of the carbonic acid diester used for the production of the polycarbonate resin (component A) used in the present invention include esters such as optionally substituted aryl groups having 6 to 20 carbon atoms, aralkyl groups, or alkyl groups having 1 to 18 carbon atoms. It is done. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (p-butylphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. preferable.

  The carbonic acid diester is preferably mixed so as to have a molar ratio of 1.02 to 0.98 with respect to the total ether diol compound, more preferably 1.01 to 0.98, and still more preferably 1.01 to 0.98. 0.99. If the molar ratio of the carbonic acid diester is more than 1.02, the carbonic acid ester residue acts as a terminal block and a sufficient degree of polymerization cannot be obtained, which is not preferable. Even when the molar ratio of carbonic acid diester is less than 0.98, a sufficient degree of polymerization cannot be obtained, which is not preferable.

  A catalyst deactivator can also be added to the polycarbonate resin (component A) obtained by the above production method. As the catalyst deactivator, known catalyst deactivators are effectively used. Among them, ammonium salts and phosphonium salts of sulfonic acid are preferable, and further, dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid is preferable. The salts of paratoluenesulfonic acid such as the above-mentioned salts and paratoluenesulfonic acid tetrabutylammonium salt are preferred. As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, para Octyl toluenesulfonate, phenyl p-toluenesulfonate and the like are preferably used, and among them, tetrabutylphosphonium dodecylbenzenesulfonate is most preferably used. These catalyst deactivators are used in an amount of 0.5 to 50 mol, preferably 0.5 to 10 mol, per mol of the polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds. It can be used in a proportion, more preferably in a proportion of 0.8 to 5 mol.

  The metal hydroxide (component B) used in the present invention can be used without particular limitation as long as it can impart flame retardancy. Magnesium hydroxide, aluminum hydroxide, calcium hydroxide, basic carbonate Examples include magnesium, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite and other compounds having a hydroxyl group or crystal water, either singly or in combination. Among these metal hydrates, at least one compound selected from the group consisting of magnesium hydroxide and aluminum hydroxide is preferable. The surface of the metal hydroxide (component B) is preferably treated with a silane coupling agent, titanic acid or a fatty acid. A coating derived from a silane coupling agent, titanic acid or a fatty acid is formed on the surface of the surface-treated metal hydroxide. By such surface treatment, not only can the decomposition of the polycarbonate resin (component A) used in the present invention be suppressed, but also the dispersibility of the metal hydroxide is improved, and the flame retardant of the polycarbonate resin and a molded product formed from the resin is improved. The property can be further improved.

  The amount of the metal hydroxide (component B) used in the present invention is 20 to 200 parts by weight, preferably 50 to 200 parts by weight, more preferably 70 to 200 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Parts, more preferably 90 to 200 parts by weight. When the amount of the metal hydroxide (component B) is less than 20 parts by weight, the flame retardancy tends to be insufficient, and when it is more than 200 parts by weight, the thermal stability and heat resistance are lowered.

  In this invention, it is preferable to mix | blend a phenol-type carbonizer (C component) further with polycarbonate resin (A component). By blending a phenol-based carbonizer, there is an advantage that flame retardancy can be expressed even if the blending ratio of the metal hydroxide (component B) is reduced.

  As the phenolic carbonizing agent, a resin containing a large amount of aromatic moieties is preferably used. Specifically, phenol resin, polyimide, polybenzimidazole, polysulfone, polyphenylene oxide, polyphenylene ether and the like can be mentioned, and phenol resin, polyphenylene oxide and polyphenylene ether are particularly preferably used. Moreover, the terpene phenol resin etc. can be preferably used as a phenol type carbonizing agent from a viewpoint that the polycarbonate resin composition of this invention contains many parts which can be induced | guided | derived from a biogenic substance.

  The amount of the phenolic carbonizing agent is preferably 5 to 30 parts by weight, more preferably 10 to 30 parts by weight, and still more preferably 10 to 25 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Moreover, the compounding quantity of the metal hydroxide (B component) at the time of using a phenol-type carbonizer becomes like this. Preferably it is 20-150 weight part, More preferably, it is 50-150 weight part, More preferably, it is 70-150 weight. Part.

  In the flame-retardant polycarbonate resin composition of the present invention, a release agent can be added as necessary. Such mold release agents are esters of alcohol and fatty acid. Among them, esters of monohydric alcohols and fatty acids or partial esters or total esters of polyhydric alcohols and fatty acids are preferable, partial esters and / or total esters of polyhydric alcohols and fatty acids are more preferable, polyhydric alcohols and fatty acids, The partial ester is more preferable. The partial ester referred to here means that a part of the hydroxyl group of the polyhydric alcohol remains without ester reaction with the fatty acid. Furthermore, esters of monohydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms and partial esters of polyhydric alcohols having 1 to 25 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms Alternatively, at least one mold release agent selected from the group consisting of total esters is preferable, and in particular, partial esters or total esters of polyhydric alcohols having 1 to 25 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms are used. Is done.

  Specific examples of the ester of a monohydric alcohol and a saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like.

  Specific examples of partial esters or total esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol diester. Dipentaerythritol such as stearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate Examples include total esters or partial esters of Toll.

  Among these esters, stearic acid monoglyceride, stearic acid diglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol distearate, propylene glycol monostearate, sorbitan monostearate, etc. Esters are preferred, stearic acid monoglyceride, stearic acid monosorbate, pentaerythritol monostearate and pentaerythritol distearate are more preferred, and stearic acid monoglyceride is particularly preferred. Such a release agent may be one kind or a mixture of two or more kinds.

  The amount of the release agent is preferably 0.01 to 0.5 parts by weight, more preferably 0.03 to 0.5 parts by weight, and further 0.03 to 0.3 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Particularly preferred is 0.03 to 0.2 parts by weight. When the release agent is within this range, improvement in releasability can be achieved while suppressing burns.

  A hindered phenol-based heat stabilizer and / or a phosphorus-based heat stabilizer may be further added to the flame-retardant polycarbonate resin composition of the present invention.

  Examples of the hindered phenol heat stabilizer include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxyalkyl ester (alkyl is Having 7 to 9 carbon atoms and having a side chain), ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene bis [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) Lopionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2'-methylenebis (6-tert-butyl-4-methylphenol, 2,2'- Isopropylidenebis (6-tert-butyl-4-methylphenol, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2-tert- Pentyl-6- (3-tert-pentyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) ) -4-methylphenyl methacrylate, 2-tert-pentyl-6- (3-tert-pentyl) 2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-butylphenyl Acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 2- [1- (2-hydroxy-3, 5-Di-tert-butylphenyl) ethyl] -4,6-di-tert-butylphenyl methacrylate and 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4 , 6-di-tert-pentylphenyl methacrylate, etc. The hindered phenol stabilizer is not only one but also two or more. Can be mixed and used.

  The amount of the hindered phenol stabilizer is preferably 0.0005 to 0.1 parts by weight, more preferably 0.001 to 0.1 parts by weight, more preferably 0.005 to 0.1 parts by weight based on 100 parts by weight of the polycarbonate resin. Part by weight is more preferable, and 0.01 to 0.1 part by weight is particularly preferable. When the hindered phenol heat stabilizer is within this range, it is possible to suppress a decrease in molecular weight or a deterioration in hue when the flame retardant polycarbonate resin composition of the present invention is molded.

  Examples of phosphorus heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di tert-butyl-4-methyl) Phenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol And diphosphite.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) ( 2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2 Examples include '-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,4 -Tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-ditert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-ditert-butylphenyl) -4,3'- Biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite And bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite. Tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (di-tert-butylphenyl) -phenyl -Phenylphosphonite is preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted. Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. The phosphorus stabilizers can be used alone or in combination of two or more.

  The amount of the phosphorus stabilizer is preferably 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.5 parts by weight, and more preferably 0.005 to 0.3 parts by weight with respect to 100 parts by weight of the polycarbonate resin. Is more preferable, and 0.01 to 0.3 part by weight is particularly preferable. When the phosphorus stabilizer is within this range, it is possible to suppress a decrease in molecular weight or a deterioration in hue when the flame-retardant polycarbonate resin composition of the present invention is molded.

  The flame retardant polycarbonate resin composition of the present invention preferably has a flexural modulus measured according to ISO178 of 4,000 to 20,000 MPa, more preferably 6,000 to 20,000 MPa, and 6,000. The range of ˜18,000 MPa is more preferable. The flame-retardant polycarbonate resin composition of the present invention can provide a molded article having excellent rigidity (flexural modulus).

  The flame retardant polycarbonate resin composition of the present invention preferably has a deflection temperature under load of 0.45 MPa measured according to ISO75, preferably in the range of 80 to 160 ° C, more preferably in the range of 90 to 150 ° C, and 100 to 150. The range of ° C is more preferable, and the range of 110 to 150 ° C is particularly preferable. It is preferable that the deflection temperature under load is in the above-mentioned range in that the balance between heat resistance and melt fluidity is good.

  In addition, the flame retardant polycarbonate resin composition of the present invention has a flame retardant level of V evaluated according to a vertical combustion test defined in US UL standard UL-94 on a 1.6 mm (1/16 inch) test piece. -2 is achieved.

  In producing the flame-retardant polycarbonate resin composition of the present invention, the production method is not particularly limited. However, a preferred method for producing the resin composition of the present invention is a method of melt-kneading each component using an extruder.

  As the extruder, a twin-screw extruder is particularly suitable, and one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder.

  It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such screens include wire meshes, screen changers, sintered metal plates (disk filters, etc.) and the like.

Furthermore, the method for supplying the component B and other additives (simply referred to as “additives” in the following examples) to the extruder is not particularly limited, but the following methods are typically exemplified.
(I) A method in which the additive is fed into the extruder independently of the component A resin.
(Ii) A method in which the additive and the resin powder of component A are premixed using a mixer such as a super mixer and then supplied to the extruder.
(Iii) A method of pre-melting and kneading the additive and component A resin into a master pellet.
(Iv) Another premixing method is a method in which a resin and an additive are uniformly dispersed in a solvent and then the solvent is removed.

  The resin composition extruded from the extruder is directly cut into pellets, or after forming the strands, the strands are cut with a pelletizer to be pelletized. Furthermore, when it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resin for optical discs and cyclic polyolefin resins for optical discs are used to narrow the pellet shape distribution, reduce miscuts, and transport or transport. Reduction of the generated fine powder and reduction of bubbles (vacuum bubbles) generated in the strands and pellets can be appropriately performed. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

  The flame-retardant polycarbonate resin composition of the present invention can be produced in various products by injection molding the pellets produced as described above. Furthermore, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets.

  In injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including those by supercritical fluid injection), insert molding, in-mold molding, depending on the purpose as appropriate. Molded articles can be obtained using injection molding methods such as mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, the resin composition of this invention can also be utilized with forms, such as various profile extrusion-molded articles, a sheet | seat, and a film, by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like.

  In addition, various function-imparting agents may be added to the flame-retardant polycarbonate resin composition of the present invention, for example, plasticizers, light stabilizers, heavy metal deactivators, lubricants, antistatic agents. UV absorbers and the like.

  A rubbery polymer may be added to the flame retardant polycarbonate resin composition of the present invention for the purpose of increasing impact resistance. Such a rubbery polymer is a polymer composed of a rubber component having a glass transition temperature of 10 ° C. or less, preferably −10 ° C. or less, more preferably −30 ° C. or less, and a polymer composed of the rubber component and other polymers. A copolymer formed by bonding polymer chains. Furthermore, the rubber component refers to a polymer containing at least 35% by weight, more preferably 45% by weight, in 100% by weight of a rubbery polymer. A practical upper limit of the rubber component content is about 90% by weight.

  More specifically, the rubbery polymer includes SB (styrene-butadiene) copolymer, ABS (acrylonitrile-butadiene-styrene) copolymer, MBS (methyl methacrylate-butadiene-styrene) copolymer, MABS (methyl methacrylate). -Acrylonitrile-butadiene-styrene) copolymer, MB (methyl methacrylate-butadiene) copolymer, ASA (acrylonitrile-styrene-acrylic rubber) copolymer, AES (acrylonitrile-ethylenepropylene rubber-styrene) copolymer, MA (Methyl methacrylate-acrylic rubber) copolymer, MAS (methyl methacrylate-acrylic rubber-styrene) copolymer, methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene Rubber - styrene copolymer, methyl methacrylate - can be exemplified (acrylic silicone IPN rubber) copolymer, and natural rubber and the like. Among them, SB copolymer, ABS copolymer, MBS copolymer, methyl methacrylate / acrylic-butadiene rubber copolymer, methyl methacrylate- (acrylic / silicone IPN rubber) copolymer, and natural rubber are selected. At least one rubbery polymer is preferred.

  The amount of the rubbery polymer used in the present invention is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight, still more preferably 1 to 10 parts by weight, particularly 100 parts by weight of the polycarbonate resin. Preferably it is 1-7 weight part. When the amount of the rubbery polymer is less than 1 part by weight, the impact strength tends to be insufficient, and when it is more than 30 parts by weight, the heat resistance or rigidity is lowered, and further flame retardancy is exhibited. I will not.

  Various flame retardant polycarbonate resin compositions of the present invention can be used in combination with various organic and inorganic fillers, fibers and the like depending on the application. Examples of the filler include carbon, talc, mica, wollastonite, montmorillonite, and hydrotalcite. Examples of the fibers include natural fibers such as kenaf, and various synthetic fibers, glass fibers, quartz fibers, and carbon fibers. Among these, natural fibers include hemp, jute, kenaf, bagasse, jute, corn fiber, bamboo fiber, wool and the like. Examples of natural fiber-derived fibers include rayon, viscose, and acetate.

  The filler and / or fiber used in the present invention is preferably 0.1 to 50 parts by weight, more preferably 1 to 50 parts by weight, still more preferably 1 to 30 parts by weight based on 100 parts by weight of the polycarbonate resin. Parts by weight.

  In addition, the flame retardant polycarbonate resin composition of the present invention includes various biological materials such as polylactic acid, aliphatic polyester, aromatic polyester, aromatic polycarbonate, polyamide, polystyrene, polyolefin, polyacryl, ABS, and polyurethane. It can also be used after being mixed with a polymer made of a starting material, a synthetic resin, rubber, etc. and alloyed.

  The flame-retardant polycarbonate resin composition of the present invention contains a part derived from a biogenic material, has both good heat resistance and thermal stability, excellent moldability, and the obtained molded product has rigidity (flexural elasticity). Rate) and transparency, and flame retardancy is good, including electrical / electronic parts, OA-related parts, various machine parts, building materials, automobile parts, various resin trays, tableware, etc. It can be used widely for various purposes.

  The following examples further illustrate the present invention. However, the present invention is not limited to these examples. Moreover, the part in an Example is a weight part and% is weight%. The evaluation was based on the following method.

(1) Specific viscosity η _sp
The pellet was dissolved in methylene chloride, the concentration was set to about 0.7 g / dL, and the temperature was measured at 20 ° C. using an Ostwald viscometer (device name: RIGO AUTO VISCOSIMETER TYPE VMR-0525 · PC). In addition, specific viscosity (eta) _sp was calculated | required from the following formula.
η _sp = t / t _o −1
t: Flow time of sample solution t _o : Flow time of solvent only

(2) Glass transition temperature It measured by DS instrument (model DSC2910) by TA Instruments using the pellet.

(3) 5% weight loss temperature It measured by T Instruments (model TGA2950) by TA Instruments using the pellet.

(4) Melt viscosity Obtained as a result of measurement using a capillary rheometer (Capillograph Model 1D) manufactured by Toyo Seiki Co., Ltd. with a capillary length of 10.0 mm, a capillary diameter of 1.0 mm, and a measurement temperature of 250 ° C. The melt viscosity at 600 sec ⁻¹ was read from the obtained Shear Rate / Viscosity curve.

(5) Flammability A 1.6 mm (1/16 inch) test piece was molded and used as an evaluation measure for flame retardancy according to a vertical combustion test defined in UL-94 of the US UL standard. Went.

(6) Flexural modulus After the pellets were dried at 120 ° C. for 12 hours, a bending test piece was formed at a cylinder temperature of 250 ° C. and a mold temperature of 90 ° C. using JSWJ-75EIII manufactured by Nippon Steel Works. The bending test was performed according to ISO178.

(7) Deflection temperature under load (0.45 MPa)
Using the bending test piece prepared in (6) above, the deflection temperature under load (0.45 MPa) defined by ISO75 was measured.

(8) Formability Molding was performed using JSWJ-75EIII manufactured by Nippon Steel Works, Ltd., and the shape of a sample plate having a thickness of 2 mm was visually evaluated (mold temperature: 80 to 110 ° C., cylinder temperature: 230 to 260 ° C.). Judgment criteria are as follows.
○: No turbidity, cracks, sink marks, or silver due to decomposition was observed.
X: Silver is observed due to turbidity, cracks, sink marks, or decomposition.

Reference Example 1 Production of Polycarbonate Resin A-1 7307 parts by weight (50 moles) of isosorbide and 10709 parts by weight (50 moles) of diphenyl carbonate were placed in a reactor, and 0.48 parts by weight of tetramethylammonium hydroxide as a polymerization catalyst ( 1 × 10 ⁻⁴ mol per mol of diphenyl carbonate component) and 5.0 × 10 ⁻⁴ parts by weight of sodium hydroxide (0.25 × 10 ⁻⁶ mol per mol of diphenyl carbonate component) It was melted by heating to 180 ° C. at normal pressure in a nitrogen atmosphere.

Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 ⁻³ MPa while the produced phenol was distilled off. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.00 × 10 ⁻³ MPa for 20 minutes while distilling off the phenol. The temperature was raised to 240 ° C. for 30 minutes and reacted for 30 minutes.

Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 ⁻³ MPa for 10 minutes and 1.33 × 10 ⁻³ MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 ⁻⁵ MPa. The temperature was gradually raised to 250 ° C., and the reaction was finally carried out at 250 ° C. and 6.66 × 10 ⁻⁵ MPa for 1 hour. The polymer after the reaction was pelletized to obtain a pellet having a specific viscosity of 0.35. The pellets had a glass transition temperature of 165 ° C., a 5% weight loss temperature of 358 ° C., and a melt viscosity of 1.79 × 10 ³ Pa · s.

Reference Example 2 Production of polycarbonate resin A-2 The reaction was carried out in the same manner as in Example 1 except that the reaction was finally carried out at 250 ° C. and 6.66 × 10 ⁻⁵ MPa for 40 minutes, and the polymer after the reaction was pelletized. A pellet having a specific viscosity of 0.29 was obtained. The pellets had a glass transition temperature of 162 ° C., a 5% weight loss temperature of 352 ° C., and a melt viscosity of 1.15 × 10 ³ Pa · s.

Examples 1-6, Comparative Example 1
The resin composition described in Table 1 was prepared as follows. Each component in the ratio shown in Table 1 was weighed and mixed uniformly, and the mixture was put into an extruder to prepare a resin composition. As the extruder, a vent type twin screw extruder (KZW15-25MG manufactured by Technobell Co., Ltd.) having a diameter of 15 mmφ was used. Extrusion conditions were a discharge rate of 14 kg / h, a screw rotation speed of 250 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 250 ° C. from the first supply port to the die part to obtain pellets. The obtained pellets were dried at 100 ° C. for 12 hours and then evaluated for each physical property.

The raw materials used in Table 1 are as follows.
(A component)
A-1: Polycarbonate resin pellets produced in Reference Example 1 A-2: Polycarbonate resin pellets produced in Reference Example 2 (Component B)
B-1: Magnesium hydroxide “Kisuma 5A” (manufactured by Kyowa Chemical Industry Co., Ltd.)
B-2: Aluminum hydroxide “B1403” (manufactured by Nippon Light Metal Co., Ltd.)
(C component)
C-1: Phenolic resin (PR-53195 manufactured by Sumitomo Bakelite Co., Ltd.)
(Other ingredients)
L-1: Stearic acid monoglyceride (Riken Vitamin Co., Ltd. Riquemar S-100A)
P-1: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (manufactured by Adeka Adeka Stub PEP-36)

Claims (8)

Flame-retardant polycarbonate resin containing 20 to 200 parts by weight of metal hydroxide (component B) with respect to 100 parts by weight of polycarbonate resin (component A) containing a carbonate constituent unit represented by the following formula (1) Composition.

  The flame-retardant polycarbonate resin according to claim 1, wherein the polycarbonate resin (component A) has a glass transition temperature (Tg) of 145 ° C to 165 ° C and a 5% weight loss temperature (Td) of 320 ° C to 400 ° C. Composition.   The flame-retardant polycarbonate resin composition according to claim 1 or 2, wherein the carbonate structural unit represented by the formula (1) is a carbonate structural unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol).   The flame-retardant polycarbonate resin composition according to any one of claims 1 to 3, wherein the metal hydroxide (component B) is at least one compound selected from the group consisting of magnesium hydroxide and aluminum hydroxide. .   The flame-retardant polycarbonate resin composition according to any one of claims 1 to 4, further comprising 5 to 30 parts by weight of a phenol-based carbonizer (C component) with respect to 100 parts by weight of the polycarbonate resin (A component). .   The flame-retardant polycarbonate resin composition according to any one of claims 1 to 5, comprising 20 to 150 parts by weight of a metal hydroxide (B component) with respect to 100 parts by weight of the polycarbonate resin (A component).   The flame-retardant polycarbonate resin composition according to any one of claims 1 to 6, wherein a flame-retardant level of UL-94 standard achieves V-2 in a molded product having a thickness of 1.6 mm.   The molded article formed from the flame-retardant polycarbonate resin composition of any one of Claims 1-7.