JP5965792B2 - Aromatic polycarbonate resin composition and molded article - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition and a molded article formed from the aromatic polycarbonate resin composition.

  Aromatic polycarbonate resin is a resin with excellent heat resistance, mechanical properties, and electrical properties. For example, automotive materials, electrical and electronic equipment materials, various household electrical equipment materials, housing materials, and other industrial parts. Widely used in materials. In particular, the flame-retardant aromatic polycarbonate resin composition is suitably used as a member of OA / information equipment such as a computer, a notebook computer, a mobile phone, a printer, and a copying machine.

As a means for imparting flame retardancy to an aromatic polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the aromatic polycarbonate resin.
However, an aromatic polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may cause a decrease in thermal stability or corrosion of a molding machine screw or a molding die during molding processing. There was a thing. In addition, the aromatic polycarbonate resin composition containing a phosphorus-based flame retardant inhibits the high transparency that is characteristic of the aromatic polycarbonate resin, and causes a decrease in impact resistance and heat resistance. There was a limit. In addition, these halogen-based flame retardants and phosphorus-based flame retardants may cause environmental pollution at the time of product disposal and recovery, and in recent years, these flame retardants can be made flame retardant without using these flame retardants. It is desired.

  Under such circumstances, in recent years, many metal salt compounds typified by organic alkali metal salt compounds and organic alkaline earth metal salt compounds have been studied as useful flame retardants. When an organometallic salt compound is used as a flame retardant, the effect can be obtained in a relatively small amount, and the mechanical properties such as impact resistance inherent in the aromatic polycarbonate resin, heat resistance, and electrical properties are not impaired. This is because flame retardancy can be imparted to.

  Examples of the flame-retarding technology of polycarbonate using a metal salt compound include, for example, a method using an alkali metal salt of perfluoroalkyl sulfonic acid having 4 to 8 carbon atoms (see Patent Document 1), and perfluoroalkane sulfone having 1 to 3 carbon atoms. A method of imparting flame retardancy to an aromatic polycarbonate resin using an alkali metal salt compound of perfluoroalkanesulfonic acid, such as a method of blending an alkali metal salt of an acid (see Patent Document 2); Using an alkali metal salt compound of an aromatic sulfonic acid such as a method of containing an acid sodium salt (see Patent Document 3) and a method of containing a non-halogenated aromatic sulfonic acid potassium salt (see Patent Document 4) A technique for imparting flame retardancy to a polycarbonate resin composition has been proposed.

  These metal salt compounds have relatively good flame retardancy for aromatic polycarbonate resins and are excellent flame retardants. However, the flame retardant performance of the aromatic polycarbonate resin is insufficient, and an aromatic polycarbonate resin having higher flame retardant performance has been desired.

  As a method for imparting flame retardancy while maintaining transparency, a polycarbonate resin that is copolymerized with a bisphenol compound having an ethynyl structure has been proposed (see Patent Document 5).

Japanese Patent Publication No. 47-40445 Japanese Patent Publication No.54-32456 JP 2000-169696 A JP 2001-181493 A WO2011 / 131366A1

Examination of the above-mentioned Patent Document 5 shows that it is effective in promoting the formation of char during combustion and has good flame retardancy, but Tg and Vicat temperature compared to conventionally known aromatic polycarbonate resins. It turned out that it is inferior to heat resistance.
An object of the present invention is to solve the problems of the prior art, and is an aromatic polycarbonate resin composition excellent in transparency, heat resistance and flame retardancy, and such aromatic polycarbonate. It is providing the molded article shape | molded from the resin composition.

（式（Ａ）中、Ｒ¹は水素原子、ハロゲン原子、炭素数１〜９の直鎖または分岐構造のアルキル基、炭素数２〜９の直鎖または分岐構造のアルケニル基、炭素数１〜９の直鎖または分岐構造のヒドロキシアルキル基、炭素数２〜９の直鎖または分岐構造のヒドロキシアルケニル基、炭素数１〜９の直鎖または分岐構造のハロアルキル基、炭素数２〜９の直鎖または分岐構造のハロアルケニル基、および置換基を有していてもよい炭素数６〜１２のアリール基から選ばれる。Ｒ⁶〜Ｒ⁹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。）
＜２＞式（Ａ）が下記式（Ｂ）で表される、＜１＞に記載の芳香族ポリカーボネート樹脂組成物。
式（Ｂ）

（式（Ｂ）中、Ｒ⁶〜Ｒ⁹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。Ｒ¹⁷〜Ｒ²¹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。）
＜３＞式（Ａ）が式（Ｃ）で表される、＜１＞に記載の芳香族ポリカーボネート樹脂組成物。
式（Ｃ）

（式（Ｃ）中、Ｒ⁶〜Ｒ⁹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。Ｒ¹⁷〜Ｒ²¹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。）
＜４＞前記（ｂ）有機スルホン酸金属塩が、フルオロアルカンスルホン酸アルカリ金属塩および／またはフルオロアルカンスルホン酸アルカリ土類金属塩である、＜１＞〜＜３＞のいずれかに記載の芳香族ポリカーボネート樹脂組成物。
＜５＞熱安定剤、酸化防止剤、難燃助剤、紫外線吸収剤、離型剤および着色剤から選択される少なくとも１種類が配合されている、＜１＞〜＜４＞のいずれかに記載の芳香族ポリカーボネート樹脂組成物。
＜６＞＜１＞〜＜５＞のいずれかに記載の芳香族ポリカーボネート樹脂組成物から成形された成形品。
＜７＞＜６＞に記載の成形品であって、厚さを１．０ｍｍの平板状としたときのヘイズ値が５％以下となる、成形品。 Means for achieving the above object are as follows.
<1> (a) With respect to 100 parts by mass of an aromatic polycarbonate resin having a terminal structure represented by the formula (A) and having a viscosity average molecular weight of 1 × 10 ^{4 to} 5 × 10 ⁴ , (b) an organic sulfone An aromatic polycarbonate resin composition comprising 0.005 parts by mass to 0.1 parts by mass of an acid metal salt.
Formula (A)

(In the formula (A), R ¹ is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, a linear or branched alkenyl group having 2 to 9 carbon atoms, 9 linear or branched hydroxyalkyl groups, straight or branched hydroxyalkenyl groups having 2 to 9 carbon atoms, straight or branched haloalkyl groups having 1 to 9 carbon atoms, straight chain having 2 to 9 carbon atoms It is selected from a chain or branched haloalkenyl group and an optionally substituted aryl group having 6 to 12 carbon atoms, wherein R ^{6 to} R ⁹ each independently represents a hydrogen atom or a carbon atom having 1 to Selected from 9 alkyl groups and oxyalkyl groups having 1 to 9 carbon atoms.)
<2> The aromatic polycarbonate resin composition according to <1>, wherein the formula (A) is represented by the following formula (B).
Formula (B)

(In Formula (B), R ^{6 to} R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms. R ¹⁷ to R ²¹ is independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms.)
<3> The aromatic polycarbonate resin composition according to <1>, wherein the formula (A) is represented by the formula (C).
Formula (C)

(In formula (C), R ^{6 to} R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms. R ¹⁷ to R ²¹ is independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms.)
<4> The fragrance according to any one of <1> to <3>, wherein (b) the organic sulfonic acid metal salt is a fluoroalkanesulfonic acid alkali metal salt and / or a fluoroalkanesulfonic acid alkaline earth metal salt. Group polycarbonate resin composition.
<5> In any one of <1> to <4>, at least one selected from a heat stabilizer, an antioxidant, a flame retardant aid, an ultraviolet absorber, a release agent, and a colorant is blended. The aromatic polycarbonate resin composition described.
<6> A molded product molded from the aromatic polycarbonate resin composition according to any one of <1> to <5>.
<7> A molded product according to <6>, wherein the molded product has a haze value of 5% or less when the thickness is 1.0 mm.

  According to the present invention, an aromatic polycarbonate resin composition excellent in transparency, heat resistance and flame retardancy can be provided.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

（式（Ａ）中、Ｒ¹は水素原子、ハロゲン原子、炭素数１〜９の直鎖または分岐構造のアルキル基、炭素数２〜９の直鎖または分岐構造のアルケニル基、炭素数１〜９の直鎖または分岐構造のヒドロキシアルキル基、炭素数２〜９の直鎖または分岐構造のヒドロキシアルケニル基、炭素数１〜９の直鎖または分岐構造のハロアルキル基、炭素数２〜９の直鎖または分岐構造のハロアルケニル基、および置換基を有していてもよい炭素数６〜１２のアリール基から選ばれる。Ｒ⁶〜Ｒ⁹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。）
ここで、式（Ａ）中、Ｒ⁶〜Ｒ⁹は、それぞれの基がベンゼン環の環状構造を形成する炭素原子の任意の位置にそれぞれ１つずつ結合していることを意味する。すなわち、ベンゼン環の環状構造を形成する炭素原子は６つあるが、そのうち１つは、−炭素炭素三重結合−Ｒ¹からなる基と結合しており、他の１つは芳香族ポリカーボネート樹脂の主鎖と結合しており、残りの４つの炭素原子がＲ⁶〜Ｒ⁹で表される基を有する。以下の一般式についても同様に考える。 The aromatic polycarbonate resin composition of the present invention has (a) a terminal structure represented by the formula (A), and 100 parts by mass of an aromatic polycarbonate resin having a viscosity average molecular weight of 1 × 10 ^{4 to} 5 × 10 ^4. On the other hand, (b) 0.005 mass part-0.1 mass part of organic sulfonic acid metal salt is contained as a flame retardant.
Formula (A)

(In the formula (A), R ¹ is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, a linear or branched alkenyl group having 2 to 9 carbon atoms, 9 linear or branched hydroxyalkyl groups, straight or branched hydroxyalkenyl groups having 2 to 9 carbon atoms, straight or branched haloalkyl groups having 1 to 9 carbon atoms, straight chain having 2 to 9 carbon atoms It is selected from a chain or branched haloalkenyl group and an optionally substituted aryl group having 6 to 12 carbon atoms, wherein R ^{6 to} R ⁹ each independently represents a hydrogen atom or a carbon atom having 1 to Selected from 9 alkyl groups and oxyalkyl groups having 1 to 9 carbon atoms.)
Here, in the formula (A), R ^{6 to} R ⁹ mean that each group is bonded to an arbitrary position of the carbon atom forming the cyclic structure of the benzene ring. That is, there are six carbon atoms that form the cyclic structure of the benzene ring, one of which is bonded to a group consisting of a —carbon carbon triple bond —R ¹ , and the other is an aromatic polycarbonate resin. The remaining four carbon atoms are bonded to the main chain and have groups represented by R ^{6 to} R ⁹ . The same applies to the following general formula.

In Formula (A), R ¹ has a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, a linear or branched hydroxyalkenyl group having 2 to 9 carbon atoms, and a substituent. An aryl group having 6 to 12 carbon atoms which may be present is preferable, an alkyl group having a linear or branched structure having 1 to 9 carbon atoms and an aryl group having 6 to 12 carbon atoms which may have a substituent are more preferable. More preferred are a methyl group, an ethyl group, and an optionally substituted phenyl group. R ¹ preferably has no substituent. The substituent which R ¹ may have is preferably selected from an alkyl group having 1 to 9 carbon atoms and an oxyalkyl group having 1 to 9 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. And a methyl group is more preferable.
In formula (A), R ^{6 to} R ⁹ are each independently preferably a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom. Is more preferable.

In the aromatic polycarbonate resin composition of the present invention, the terminal triple bond group not only can impart excellent flame retardancy to the molded product in order to promote the cyclization reaction due to heat during combustion, A molded product having a low haze value, that is, excellent transparency can be obtained. As a site containing a triple bond group in the structure of the aromatic polycarbonate resin, in addition to the terminal group, a structure that is copolymerized in the molecular chain of the aromatic polycarbonate resin can be considered, but the triple bond group is included in the molecular chain. When it has, glass transition temperature (Tg) falls and it may cause the heat resistant fall of a molded article. In addition, by having a carbon-carbon triple bond at the end group as in the present invention, it is possible to cyclize between end groups by heat during combustion, thus promoting the formation of a carbonized layer in the combustion process, It can be expected that the flame retardant performance is exhibited more effectively than the structure containing a triple bond group.
Furthermore, in the aromatic polycarbonate resin composition of the present invention, the addition ratio of (b) organic sulfonic acid metal salt blended as a flame retardant does not exceed 0.1 parts by mass, so the haze value is low. A molded product having excellent transparency can be obtained. In addition, since organic sulfonic acid metal salts are used as flame retardants, it may cause a decrease in thermal stability, as in the case of using halogen-based flame retardants or phosphorus-based flame retardants. There will be no problems such as corrosion of the mold, hindering high transparency, and deterioration of impact resistance and heat resistance.

（式（Ｂ）中、Ｒ⁶〜Ｒ⁹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。Ｒ¹⁷〜Ｒ²¹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。） In the aromatic polycarbonate resin used in the present invention, the formula (A) is preferably represented by the following formula (B).
Formula (B)

(In Formula (B), R ^{6 to} R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms. R ¹⁷ to R ²¹ is independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms.)

In formula (B), R ^{6 to} R ⁹ have the same meaning as R ^{6 to} R ⁹ in formula (A), and the preferred range is also the same.
In the formula (B), R ^{17 to} R ²¹ are each independently preferably a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom. Is more preferable.

（式（Ｃ）中、Ｒ⁶〜Ｒ⁹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。Ｒ¹⁷〜Ｒ²¹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。） The aromatic polycarbonate resin used in the present invention is more preferably an aromatic polycarbonate resin having a terminal structure containing a phenylethynylphenol group at the terminal meta position of the aromatic polycarbonate resin. By coordinating the phenylethynyl group at the meta position, while maintaining the effects of the present invention such as flame retardancy, the production of colored substances can be effectively suppressed, and yellowing at high temperatures can be suppressed. it can. Specifically, in the aromatic polycarbonate resin used in the present invention, the formula (A) is preferably represented by the formula (C).
Formula (C)

(In formula (C), R ^{6 to} R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms. R ¹⁷ to R ²¹ is independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms.)

In formula (C), R ^{6 to} R ⁹ have the same meaning as R ^{6 to} R ⁹ in formula (A), and the preferred range is also the same.
Wherein (C), R ¹⁷ ~R ²¹ has the same meaning as R ¹⁷ to R ²¹ in Formula (B), the preferred range is also the same.

  Thus, by arranging the terminal carbon-carbon triple bond group at the meta position, it is possible to obtain a molded piece excellent in hue in which yellowing is effectively suppressed.

（式（Ｉ）中、Ｒ¹は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜９の直鎖または分岐構造のアルキル基、炭素数２〜９の直鎖または分岐構造のアルケニル基、炭素数１〜９の直鎖または分岐構造のヒドロキシアルキル基、炭素数２〜９の直鎖または分岐構造のヒドロキシアルケニル基、炭素数１〜９の直鎖または分岐構造のハロアルキル基、炭素数２〜９の直鎖または分岐構造のハロアルケニル基、および置換基を有していてもよい炭素数６〜１２のアリール基から選ばれる。Ｒ²〜Ｒ⁵は、それぞれ独立に、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、置換基を有してもよい炭素数１〜９のアルキル基、置換基を有してもよい炭素数１〜５のアルコキシ基、置換基を有してもよい炭素数６〜１２のアリール基、置換基を有してもよい炭素数２〜５のアルケニル基、または、置換基を有してもよい炭素数７〜１７のアラルキル基を表す。Ｒ⁶〜Ｒ⁹は、それぞれ独立に、水素原子、炭素原子数１〜９のアルキル基、および、炭素原子数１〜９のオキシアルキル基から選ばれる。ｎは１５〜２００の整数である。Ｘは、下記式群（Ｉ−１）から選択される。）
式群（Ｉ−１）

（式群（Ｉ−１）中、Ｒ¹⁰およびＲ¹¹は、それぞれ独立に、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、置換基を有してもよい炭素数１〜９のアルキル基、置換基を有してもよい炭素数１〜５のアルコキシ基、置換基を有してもよい炭素数６〜１２のアリール基、置換基を有してもよい炭素数２〜５のアルケニル基、または、置換基を有してもよい炭素数７〜１７のアラルキル基である。Ｒ¹⁰およびＲ¹¹は互いに結合して炭素環または複素環を形成していてもよい。Ｒ¹²〜Ｒ¹⁵は、それぞれ独立に、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、置換基を有してもよい炭素数１〜９のアルキル基、置換基を有してもよい炭素数１〜５のアルコキシ基、または、置換基を有してもよい炭素数６〜１２のアリール基である。Ｒ¹⁶は、置換基を有してもよい炭素数１〜９のアルキレン基であり、ａは０〜２０の整数を表し、ｂは１〜５００の整数を表す。） The aromatic polycarbonate resin used in the present invention is more preferably an aromatic polycarbonate resin represented by the following formula (I).
Formula (I)

(In formula (I), each R ¹ is independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, or a linear or branched alkenyl group having 2 to 9 carbon atoms. , A linear or branched hydroxyalkyl group having 1 to 9 carbon atoms, a linear or branched hydroxyalkenyl group having 2 to 9 carbon atoms, a linear or branched haloalkyl group having 1 to 9 carbon atoms, a carbon number It is selected from 2 to 9 linear or branched haloalkenyl groups and optionally substituted aryl groups having 6 to 12 carbon atoms, R ^{2 to} R ⁵ each independently represents a hydrogen atom, A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted alkyl group having 1 to 9 carbon atoms, an optionally substituted alkoxy group having 1 to 5 carbon atoms, and a substituent. An aryl group having 6 to 12 carbon atoms, An alkenyl group having 2 to 5 carbon atoms which may have a substituent, or an aralkyl group having 7 to 17 carbon atoms which may have a substituent, wherein R ^{6 to} R ⁹ are each independently hydrogen; An atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms, n is an integer of 15 to 200. X is from the following formula group (I-1). Selected.)
Formula group (I-1)

(In formula group (I-1), R < ¹⁰ > and R <^11> are respectively independently C1-C9 which may have a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a substituent. An alkyl group, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, and 2 to 5 carbon atoms which may have a substituent alkenyl group or a substituted aralkyl group which may carbons 7 to 17 .R ¹⁰ and R ¹¹ optionally form a carbocyclic or heterocyclic ring bonded to each other .R ^12, To R ¹⁵ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted alkyl group having 1 to 9 carbon atoms, or an optionally substituted carbon atom. An alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms which may have a substituent; R ¹⁶ is an optionally substituted alkylene group having 1 to 9 carbon atoms, a represents an integer of 0 to 20, and b represents an integer of 1 to 500.)

The repeating units in formula (I) may be the same or different.
In formula (I), R ¹ has the same meaning as R ¹ in formula (A), is synonymous preferable ranges. R ^{1 at the} two ends in formula (I) may be the same or different. Usually the same.
In formula (I), R ^{2 to} R ⁵ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted alkyl group having 1 to 9 carbon atoms, or a substituent. An alkoxy group having 1 to 5 carbon atoms which may have a group, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl having 7 to 17 carbon atoms which may have a substituent Group is preferable, a hydrogen atom, and an optionally substituted alkyl group having 1 to 9 carbon atoms is more preferable, and a hydrogen atom is more preferable. The substituents that R ^{2 to} R ⁵ may have are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, An alkyl group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms are more preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. In formula (I), two R ² are present in one repeating unit, but they may be the same or different. The same applies to other codes such as R ³ .
Wherein (I), R ⁶ ~R ⁹ has the same meaning as R ⁶ to R ⁹ in Formula (A), the preferred range is also the same.
In formula (I), n is preferably an integer of 15 to 200, and more preferably an integer of 20 to 150.

が好ましく、

がより好ましい。 In formula group (I-1), X represents

Is preferred,

Is more preferable.

In formula group (I-1), R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl having 1 to 9 carbon atoms that may have a substituent. Group, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or 7 to 7 carbon atoms which may have a substituent 17 is preferably an aralkyl group, more preferably a hydrogen atom, an optionally substituted alkyl group having 1 to 9 carbon atoms, and an optionally substituted aryl group having 6 to 12 carbon atoms, a hydrogen atom, An alkyl group having 1 to 9 carbon atoms which may have a substituent is more preferable. The substituents that R ¹⁰ and R ¹¹ may have include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an optionally substituted alkyl group having 1 to 9 carbon atoms, and a substituent. Preferred are an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 17 carbon atoms which may have a substituent. , A hydrogen atom, an optionally substituted alkyl group having 1 to 9 carbon atoms, and an optionally substituted aryl group having 6 to 12 carbon atoms, more preferably a hydrogen atom and a substituent. More preferred is an alkyl group having 1 to 9 carbon atoms.
In formula group (I-1), R ¹² and R ¹³ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl having 1 to 9 carbon atoms that may have a substituent. Group, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent is preferable, and may have a hydrogen atom or a substituent. A C1-C9 alkyl group or a C6-C12 aryl group which may have a substituent is more preferable, and a hydrogen atom and a C1-C9 alkyl group which may have a substituent are preferable. Further preferred. The substituent that R ¹² and R ¹³ may have is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, A C1-C5 alkyl group and a C1-C5 alkoxy group are more preferable, and a C1-C5 alkyl group is still more preferable.
In the formula group (I-1), R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a C 1-9 alkyl which may have a substituent. Group, an alkoxy group having 1 to 5 carbon atoms which may have a substituent, or an aryl group having 6 to 12 carbon atoms which may have a substituent is preferable, and may have a hydrogen atom or a substituent. A C1-C9 alkyl group or a C6-C12 aryl group which may have a substituent is more preferable, and a hydrogen atom and a C1-C9 alkyl group which may have a substituent are preferable. Further preferred. The substituent that R ¹⁴ and R ¹⁵ may have is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, A C1-C5 alkyl group and a C1-C5 alkoxy group are preferable, and a C1-C5 alkyl group is more preferable.
In the formula group (I-1), R ¹⁶ is preferably an alkylene group having 1 to 9 carbon atoms which may have a substituent, and more preferably an alkylene group having 1 to 5 carbon atoms which may have a substituent. Preferably, ethylene and propylene are more preferable. The substituent that R ¹⁶ may have is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, 5 alkyl groups and C1-C5 alkoxy groups are more preferable, and C1-C5 alkyl groups are more preferable.
In formula group (I-1), a is preferably an integer of 0 to 20, and more preferably an integer of 0 to 1.
In formula group (I-1), b is preferably an integer of 1 to 200, and more preferably an integer of 10 to 200.

The aromatic polycarbonate resin represented by the formula (I) is preferably an aromatic polycarbonate resin represented by the formula (II).
Formula (II)

R ^{2 to} R ⁵ in the formula (II) are each independently synonymous with R ^{2 to} R ⁵ in the formula (I), and a preferred range is also synonymous.
R < ⁶ > -R < ⁹ > in Formula (II) is synonymous with R < ⁶ > -R < ⁹ > in Formula (A), respectively, and its preferable range is also synonymous.
In formula (II), R ^{17 to} R ²¹ have the same meaning as R ^{17 to} R ²¹ in formula (B), and the preferred range is also the same.
N in formula (II) has the same meaning as n in formula (I), and the preferred range is also the same.
X in formula (II) has the same meaning as X in formula (I), and the preferred range is also the same.

The viscosity average molecular weight of the aromatic polycarbonate resin used in the present invention is 1 × 10 ^{4 to} 5 × 10 ⁴ , and preferably 1.2 × 10 ^{4 to} 3 × 10 ⁴ . By setting it as such a range, it becomes possible to keep the balance of the favorable fluidity | liquidity at the time of shaping | molding, and mechanical strength more effectively.

  Viscosity average molecular weight (Mv) was measured by measuring 0.2 g / deciliter of a solution of aromatic polycarbonate resin in dichloromethane with a Ubbelohde capillary viscometer at a temperature of 20 ° C., and using a Haggins constant of 0.45 and an intrinsic viscosity [η] deciliter / Gram is calculated and calculated by the following formula.

  The aromatic polycarbonate resin used in the present invention can be synthesized based on a known method. For example, various synthetic methods including an interfacial polymerization method, a pyridine method, a transesterification method, and a ring-opening polymerization method of a cyclic carbonate compound are used. Can be mentioned. Specifically, an aromatic dihydroxy compound or a small amount thereof and a small amount of a polyhydroxy compound, carbonyl chloride generally known as phosgene, or a carbonic acid diester represented by dimethyl carbonate or diphenyl carbonate, carbon monoxide or carbon dioxide It is a polymer or copolymer of a linear or branched thermoplastic aromatic polycarbonate obtained by reacting with a carbonyl compound. The terminal structure of the aromatic polycarbonate resin used in the present invention can be formed using a molecular weight modifier or a terminal terminator having a group containing a specific triple bond.

  Examples of the aromatic dihydroxy compound as a raw material include 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], bis (4-hydroxyphenyl) -p-diisopropylbenzene, 4,4′-dihydroxydiphenyl, 2 , 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethyl) Phenyl) propane, 2,2-bis (4-hydroxy-3,5-diphenylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4- Hydroxyphenyl) pentane, 2,4′-dihydroxy-diphenylmethane, bis- (4-hydroxyphenyl) methane, bi Su- (4-hydroxy-3-nitrophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) ) Cyclohexane [= bisphenol Z], bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy- 3,3′-dimethyldiphenyl ether, 4,4′-dihydroxy-2,5-diethoxydiphenyl ether, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy- 3-methylphenyl) cyclohexane, 1-phenyl-1,1-bis (4 Hydroxy-3-methylphenyl) ethane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and the like can be mentioned, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) is particularly preferable. Propane [bisphenol A] and 1,1-bis (4-hydroxyphenyl) cyclohexane [bisphenol Z]. These aromatic dihydroxy compounds can be used alone or in admixture of two or more. In addition, as a part of the dihydroxy compound, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound, or a polymer or oligomer having a siloxane structure and containing both terminal phenolic OH groups may be used. May be.

  In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris ( 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1 A polyhydroxy compound represented by tris (4-hydroxyphenyl) ethane or the like, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7 -Some of the aromatic dihydroxy compounds described above, such as dichlorouisatin bisphenol and 5-bromoisatin bisphenol It may be used by, usage, 0.01 to 10 mol%, preferably from 0.1 to 3 mol%.

  Specific examples of the compound constituting the terminal group containing a specific triple bond include ethynylphenol, methylethynylphenol, ethylethynylphenol, phenylethynylphenol, methylphenylethynylphenol, dimethylphenylethynylphenol, bromophenylethynylphenol, chlorophenylethynyl. Phenol, naphthylethynylphenol, ethynylcresol, methylethynylcresol, ethylethynylcresol, phenylethynylcresol, methylphenylethynylcresol, dimethylphenylethynylcresol, bromophenylethynylcresol, chlorophenylethynylcresol, naphthylethynylcresol, ethynylxylenol, methylethynylxylenol , Ethylethynylxyleno , Phenylethynyl xylenol, methylphenylethynyl xylenol, dimethylphenyl ethynyl xylenol, bromo phenylethynyl xylenol, chlorophenylethynyl xylenol, etc. naphthyl ethynyl xylenol.

  In the reaction by the interfacial polymerization method, in the presence of an organic solvent inert to the reaction, an alkaline aqueous solution, the pH is usually kept at 10 or more, an aromatic dihydroxy compound and a molecular weight modifier (terminal stopper), if necessary Using an antioxidant for antioxidants of aromatic dihydroxy compounds, reacting with phosgene, adding a polymerization catalyst such as tertiary amine or quaternary ammonium salt, and conducting interfacial polymerization A polycarbonate resin can be obtained. The addition of the molecular weight regulator is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction. The reaction temperature is 0 to 35 ° C., and the reaction time is several minutes to several hours.

  Here, examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene. be able to. As a molecular weight regulator or a terminal terminator, a compound having a monovalent phenolic hydroxyl group can be used in combination with the compound containing the triple bond listed above, as long as the effects of the present invention are not impaired. Examples include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. As a polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, pyridine; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Can be mentioned.

  The reaction by the transesterification method is a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound. Usually, the molecular weight and terminal hydroxyl group amount of the desired aromatic polycarbonate resin are determined by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound or adjusting the degree of vacuum during the reaction. The amount of terminal hydroxyl groups has a large effect on the thermal stability, hydrolysis stability, color tone, etc. of the aromatic polycarbonate resin, and is preferably 1000 ppm or less, more preferably 700 ppm, in order to have practical physical properties. It is as follows. It is common to use an equimolar amount or more of a carbonic acid diester with respect to 1 mol of the aromatic dihydroxy compound, and it is preferably used in an amount of 1.01-1.30 mol.

Examples of carbonic acid diesters include substitution of dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate, diphenyl carbonate or di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-p-chlorophenyl carbonate. Examples include diphenyl carbonate. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable.
These carbonic acid diester compounds can be used alone or in admixture of two or more.

When synthesizing an aromatic polycarbonate resin by a transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, but alkali metal compounds and / or alkaline earth metal compounds are mainly used. Auxiliary basic boron compounds, basic phosphorus compounds, basic ammonium compounds, or amine-based catalysts are used. It is also possible to use a basic compound such as a compound in combination. In the transesterification reaction using such raw materials, the reaction is performed at a temperature of 100 to 320 ° C., and finally, a by-product such as an aromatic hydroxy compound under a reduced pressure of 2.7 × 10 ² Pa ( ² mmHg) or less. A method in which a melt polycondensation reaction is performed while removing substances. The melt polycondensation can be carried out batchwise or continuously, but the aromatic polycarbonate resin used in the present invention is preferably carried out continuously from the viewpoint of stability and the like. In the transesterification method, it is preferable to use a compound that neutralizes the catalyst, for example, a sulfur-containing acidic compound, or a derivative formed therefrom, as a deactivator of the catalyst in the aromatic polycarbonate resin. It is added in the range of 0.5 to 10 equivalents, preferably 1 to 5 equivalents relative to the alkali metal of the catalyst, and is usually added in the range of 1 to 100 ppm, preferably 1 to 20 ppm relative to the aromatic polycarbonate resin.

  The aromatic polycarbonate resin obtained by the above method is prepared as an aromatic polycarbonate resin composition. Flakes of an aromatic polycarbonate resin composition can be obtained, for example, by dropping a methylene chloride solution containing an aromatic polycarbonate resin obtained by an interfacial polymerization method into warm water kept at 45 ° C. and evaporating and removing the solvent. Alternatively, the methylene chloride solution containing the aromatic polycarbonate resin obtained by the interfacial polymerization method is put into methanol, and the precipitated polymer is filtered and dried. Alternatively, The methylene chloride solution containing the aromatic polycarbonate resin obtained by the interfacial polymerization method can be obtained by stirring and grinding while stirring at 40 ° C. with a kneader and then removing the solvent with hot water at 95 ° C. or higher.

  If necessary, after isolating the aromatic polycarbonate resin based on a well-known method, for example, a well-known strand-type cold cut method (forms a once melted aromatic polycarbonate resin composition into a strand shape, cooled, A method of cutting into a predetermined shape and pelletizing), a hot-cut method in the air hot cut method (a method of cutting an aromatic polycarbonate resin composition once melted into pellets before being exposed to water in the air) ), An underwater hot cut type hot cut method (a method in which an aromatic polycarbonate resin composition once melted is cut in water and simultaneously cooled and pelletized) to obtain pellets of an aromatic polycarbonate resin composition it can. In addition, it is preferable to dry the obtained aromatic polycarbonate resin composition pellet based on methods, such as drying using a hot air drying furnace, a vacuum drying furnace, and a dehumidification drying furnace as needed.

The aromatic polycarbonate resin composition of the present invention has an aromatic polycarbonate resin used in the present invention (having a terminal structure represented by the formula (A) as necessary, unless the desired physical properties are significantly impaired. A resin other than the aromatic polycarbonate resin having a viscosity average molecular weight of 1 × 10 ^{4 to} 5 × 10 ⁴ may be contained. Examples of such other resins include polycarbonate resins other than the aromatic polycarbonate resin used in the present invention, polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate resin (PBT resin), and the like. Thermoplastic polyester resin: polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), styrene resin such as methyl methacrylate-styrene copolymer (MS resin); methyl Core / shell type elastomer such as methacrylate-acrylic rubber-styrene copolymer (MAS), elastomer such as polyester elastomer; cyclic cycloolefin resin (COP resin), cyclic cycloolefin (COP) Polyolefin resins such as coalescence resins; Polyamide resins (PA resins); Polyimide resins (PI resins); Polyetherimide resins (PEI resins); Polyurethane resins (PU resins); Polyphenylene ether resins (PPE resins); Polyphenylene sulfide resins (PPS) Resin); polysulfone resin (PSU resin); polymethacrylate resin (PMMA resin); polycaprolactone and the like.
The blending ratio of the other resin components in the aromatic polycarbonate resin composition of the present invention is preferably 10% by mass or less of the total resin components, and is preferably substantially free of resin components other than the polycarbonate resin. . “Substantially not containing” means, for example, not actively blending as a resin component. If an example is given, it is 1 mass% or less of all the resin components.

In the aromatic polycarbonate resin composition of the present invention, an organic sulfonic acid metal salt is blended as a flame retardant.
Examples of organic sulfonic acid metal salts include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. These may be used alone or in combination of two or more. Moreover, as a metal salt, an alkali metal salt and an alkaline-earth metal salt are preferable.
Examples of the alkali metal include sodium, lithium, potassium, rubidium, and cesium. Examples of alkaline earth metals include calcium and strontium. The preferred metal of the organic sulfonic acid metal salt used in the present invention is an alkali metal such as sodium, potassium, rubidium and cesium, more preferably sodium and potassium. By adopting such a metal, it is possible to effectively promote formation of a carbonized layer during combustion and maintain high transparency.

As the aliphatic sulfonate, a fluoroalkane-sulfonic acid metal salt is preferable, and a perfluoroalkane-sulfonic acid metal salt is more preferable.
Examples of the fluoroalkane-sulfonic acid metal salt include alkali metal salts and alkaline earth metal salts, and alkali metal salts are preferred.
As carbon number of a fluoroalkanesulfonic acid metal salt, 1-8 are preferable and 2-4 are more preferable. By setting it as such a range, the effect that high transparency can be maintained is acquired.
Specific examples of preferred fluoroalkane-sulfonic acid metal salts include perfluorobutane-sodium sulfonate, potassium perfluorobutane-sulfonate, sodium perfluoroethane-sulfonate, potassium perfluoroethane-sulfonate, and the like. it can.

Examples of the aromatic sulfonic acid metal salt include alkali metal salts and alkaline earth metal salts, and alkali metal salts are preferable.
Specific examples of the aromatic sulfonesulfonic acid alkali metal salt include 3,4-dichlorobenzenesulfonic acid sodium salt, 2,4,5-trichlorobenzenesulfonic acid sodium salt, benzenesulfonic acid sodium salt, diphenylsulfone-3-sulfone. Sodium salt of acid, potassium salt of diphenylsulfone-3-sulfonic acid, sodium salt of 4,4'-dibromodiphenyl-sulfone-3-sulfonic acid, potassium of 4,4'-dibromophenylsulfone-3-sulfonic acid Salt, disodium salt of diphenylsulfone-3,3'-disulfonic acid, dipotassium salt of diphenylsulfone-3,3'-disulfonic acid, sodium salt of dodecylbenzenesulfonic acid, potassium salt of dodecylbenzenesulfonic acid, p-toluenesulfonic acid Potassium salt, p-styrene Sulfonic acid potassium salt and the like.

The organic sulfonic acid metal salt used in the present invention is a potassium salt of diphenylsulfone-3-sulfonic acid, potassium salt of p-toluenesulfonic acid, potassium salt of p-styrenesulfonic acid, dodecylbenzene, particularly from the viewpoint of improving transparency. A sulfonic acid potassium salt is preferable, and a potassium salt of diphenylsulfone-3-sulfonic acid is more preferable.
In addition, as above-mentioned, although the addition mass of the organic sulfonic acid metal salt with respect to 100 mass parts of aromatic polycarbonate resin is 0.005 mass part-0.1 mass part, Preferably it is 0.01 mass part-0.00. 1 part by mass, more preferably 0.03 part by mass to 0.09 part by mass.
Moreover, in this invention, you may mix | blend flame retardants other than organic sulfonic acid metal salt, However, It is preferable that the compounding quantity of another flame retardant is 0.001 mass% or less of the total mass of a composition.

Various additives may be blended in the aromatic polycarbonate resin composition of the present invention without departing from the spirit of the present invention. Examples of the additive include at least one additive selected from the group consisting of a heat stabilizer, an antioxidant, a flame retardant aid, an ultraviolet absorber, a release agent, and a colorant.
In addition, an antistatic agent, a fluorescent whitening agent, an antifogging agent, a fluidity improving agent, a plasticizer, a dispersing agent, an antibacterial agent and the like may be added as long as desired physical properties are not significantly impaired.

  Examples of the heat stabilizer include phenol-based, phosphorus-based, and sulfur-based heat stabilizers. Specifically, phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, acidic calcium pyrophosphate; potassium phosphate , Sodium phosphate, cesium phosphate, zinc phosphate, etc., Group 1 or Group 10 metal phosphates; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like. Alternatively, the phosphite compound (a), phosphorous acid (b), and at least one ester in the molecule esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms Mention may be made of at least one selected from the group of tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di-phosphonite (c). Specific examples of the phosphite compound (a) include trioctyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tris (monononylphenyl) phos Phyto, Tris (monononyl / dinonyl phenyl) phosphite, Trisnonyl phenyl phosphite, Tris (octylphenyl) phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, Trinonyl phosphite, Didecyl Monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, bis (2,4-di-tert-butyl) Ruphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, diphenylpenta Erythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (Nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) Mention may be made of pentaerythritol diphosphite and the like. These may be used alone or in combination of two or more.

  Specific examples of the organic phosphite compound include, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10”, and “JP-351” manufactured by Johoku Chemical Industry Co., Ltd. , “JP-360”, “JP-3CP”, “Irgaphos 168” manufactured by Ciba Specialty Chemicals, and the like.

  Examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate, and the like.

  When blended, the addition ratio of the heat stabilizer is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more with respect to 100 parts by mass of the aromatic polycarbonate resin. In addition, it is 1 part by mass or less, preferably 0.7 part by mass or less, more preferably 0.5 part by mass or less. If the amount of the heat stabilizer is too small, the heat stabilizing effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

  Examples of the antioxidant include phenolic antioxidants, hindered phenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, and the like. Specifically, 2,6-di-tert-butyl-4-methylphenol, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, n-octadecyl-3- (3 ′, 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} 2,4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide) ), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphoate, 3,3 ′, 3 ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(mesitylene-2,4,6-triyl) tri-p-cle 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2- Ilamino) phenol, etc. Specific examples of phenolic antioxidants include “Irganox 1010” (registered by Ciba Specialty Chemicals). Trademark, hereinafter the same), "Irganox 1076", manufactured by Adeka Corporation "ADK STAB AO-50" can be like "ADK STAB AO-60" is given.

  When blended, the addition ratio of the antioxidant is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, and 1 part by mass or less, preferably 100 parts by mass of the aromatic polycarbonate resin. Is 0.5 parts by mass or less. If the addition ratio of the antioxidant is below the lower limit, the effect as an antioxidant may be insufficient, and if the addition ratio of the antioxidant exceeds the upper limit, the effect reaches a peak and is economical. There is a possibility of disappearing.

  For example, a silicone compound can be added as a flame retardant aid. As a silicone compound, what has a phenyl group in a molecule | numerator is preferable. By having a phenyl group, the dispersibility of the silicone compound in the polycarbonate is improved, and the transparency and flame retardancy are excellent. The weight average molecular weight of the silicone compound is preferably 450 to 5000, and more preferably 750 to 4000, more preferably 1000 to 3000, and particularly preferably 1500 to 2500. By making the weight average molecular weight 450 or more, the production becomes easy, the adaptation to industrial production becomes easy, and the heat resistance of the silicone compound is hardly lowered. Conversely, by setting the weight average molecular weight of the silicone compound to 5,000 or less, the dispersibility in the polycarbonate resin composition is less likely to be reduced, and the flame retardancy and the mechanical properties in the aromatic polycarbonate resin composition are further reduced. It tends to be effectively suppressed.

  When blended, the addition ratio of the flame retardant aid is, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and 7.5 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Hereinafter, it is preferably 5 parts by mass or less. If the addition rate of flame retardant aid is below the lower limit, flame retardancy may be insufficient, and if the addition rate of flame retardant aid exceeds the upper limit, appearance defects such as delamination will occur and transparency , The flame retardancy reaches its peak, and it may not be economical.

  In addition to inorganic UV absorbers such as cerium oxide and zinc oxide, UV absorbers include benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds, phenyl salicylates Examples thereof include organic ultraviolet absorbers such as compounds. Of these, benzotriazole-based and benzophenone-based organic ultraviolet absorbers are preferred. In particular, specific examples of benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-) Methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2′-hydroxy-3 ′ , 5′-di-tert-amyl) -benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- ( , 1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 -[(Hexyl) oxy] -phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 '-(1,4-phenylene) bis [4H-3,1-benzoxazin-4-one], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester, 2- (2H-benzotriazole -2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylmethyl) phenol, 2- [5-chloro (2H)- Nzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol, 2- ( 2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrabutyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 1,3,3-tetrabutyl) phenol], [methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate, etc. Can be mentioned. Two or more of these may be used in combination. Of the above, preferably 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2,2′-methylene-bis [4- (1,1,3,3-tetramethylbutyl) ) -6- (2N-benzotriazol-2-yl) phenol]. Specific examples of the benzophenone ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy- Benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4 And 4'-tetrahydroxy-benzophenone. Specific examples of phenyl salicylate UV absorbers include phenyl salicylate and 4-tert-butyl-phenyl salicylate. Furthermore, as specific examples of the triazine ultraviolet absorber, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4 , 6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol and the like. Specific examples of hindered amine ultraviolet absorbers include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

  The proportion of the ultraviolet absorber added is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and preferably 3 parts by mass or less, preferably 100 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Is 1 part by mass or less. If the addition ratio of the UV absorber is below the lower limit, the effect of improving the weather resistance may be insufficient, and if the addition ratio of the UV absorber exceeds the upper limit, mold deposits, etc. will occur and mold contamination May cause.

Examples of the release agent include release agents such as carboxylic acid esters, polysiloxane compounds, and paraffin wax (polyolefin type). Specific examples include at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oils. be able to. Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes an alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melissic acid, tetrariacontanoic acid, montanic acid, Examples include glutaric acid, adipic acid, azelaic acid, and the like. As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, the aliphatic includes alicyclic compounds. Specific examples of alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. be able to. In addition, said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound. Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like. Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the alicyclic hydrocarbon is also included in the aliphatic hydrocarbon. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance or a mixture of components and various molecular weights as long as the main component is within the above range. Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.
When added, the addition ratio of the release agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and 2 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin. More preferably, it is 1 part by mass or less. If the addition ratio of the release agent is below the lower limit value, the effect of the release property may not be sufficient, and if the addition ratio of the release agent exceeds the upper limit value, hydrolysis resistance decreases, gold during injection molding Mold contamination may occur.

Examples of the dye / pigment as a colorant include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, and zinc-iron. Oxide pigments such as chrome brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, copper-iron black; chromic pigments such as yellow lead and molybdate orange; ferrocyans such as bitumen And pigments. Further, as organic pigments and organic dyes as colorants, for example, phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone And condensed polycyclic dyes such as dioxazine, isoindolinone, and quinophthalone; quinoline, anthraquinone, heterocyclic, and methyl dyes. Of these, titanium oxide, carbon black, cyanine, quinoline, anthraquinone, phthalocyanine dyes and the like are preferable from the viewpoint of thermal stability. In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.
When added, the proportion of the colorant added is, for example, 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin. If the addition ratio of the colorant is too large, the impact resistance may not be sufficient.

  The molded product of the present invention is a molded product molded from the aromatic polycarbonate resin composition of the present invention including the various preferred forms and configurations described above. There is no limitation on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application. Specifically, as molded products, electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods / miscellaneous goods, parts for lighting equipment, various household use Examples include parts such as electrical products, housings for electrical appliances, containers, covers, storage units, cases, covers and cases for lighting fixtures, and the like. Examples of electrical and electronic equipment include personal computers, game machines, television receivers, display devices such as liquid crystal display devices and plasma display devices, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic devices A dictionary, a camera, a video camera, a mobile phone, a battery pack, a drive or reading device for a recording medium, a mouse, a numeric keypad, a CD player, an MD player, a portable radio / audio player, and the like. In addition, examples of the molded article include an electric signboard, a liquid crystal backlight, an illumination display, a traffic sign, a sign board, a screen, a car part such as a reflector and a meter part, a toy, and a decorative article.

  The manufacturing method of the molded article of the present invention is not particularly limited, and a molding method generally adopted for the polycarbonate resin composition can be arbitrarily adopted. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, etc. Can be mentioned. A molding method using a hot runner method can also be used.

  The flame retardancy of the aromatic polycarbonate resin composition was evaluated by conditioning an Izod test piece obtained by the method described later for 48 hours in a temperature-controlled room at a temperature of 23 ° C. and a relative humidity of 50%, and JIS K-7201. The test is conducted in accordance with “Method for Combustion Test of Polymer Material by Oxygen Index Method”. In this test, those having a combustion oxygen index (LOI value) of 26 or more are considered to have flameproofing properties (self-extinguishing properties). In the present invention, the flame retardancy can be 30 or more, and can be 40 or more.

  The haze value as a transparency evaluation is based on JIS K-7136 "Plastics-Determination of haze of transparent material". A plate-shaped product produced by the method described later is used as a test piece. Measured with an NDH-2000 turbidimeter manufactured by Color Industries. Haze is used as a measure of the white turbidity of the resin, and the smaller the value, the higher the transparency. In Table 1 to be described later, it is expressed as “transparency”.

  When the molded product molded from the aromatic polycarbonate resin composition of the present invention is, for example, a molded product having a flat plate portion having a thickness of 1.0 mm, the haze value can be 5% or less, and It can be 3% or less, and further can be 1% or less.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to an Example, The various numerical value and material in an Example are illustrations.

<Synthesis of p-phenylethynylphenol (A)>
In a 500 ml three-necked flask containing a stirring bar under a nitrogen stream, 8.8278 g (0.040 mol) of 4-iodophenol, 0.4038 g (0.58 mmol) of a palladium catalyst, 0.1107 g (0.58 mmol) of a copper catalyst, 0.1515 g (0.58 mmol) of phenylphosphine, 5.3426 g (0.052 mmol) of ethynylbenzene and 300 ml of triethylamine were added and reacted at room temperature for 24 hours.
The solution was filtered, extracted with diethyl ether, triethylamine as a solvent was removed with HCl, washed with distilled water, dried at 40 ° C. under reduced pressure for 6 hours, and purified by sublimation.
As a result, 6.31 g (yield: 81%) of white powder was obtained. ¹ HNMR and ¹³ CNMR of the obtained compound were measured, and from the assignment of all signals, it was confirmed that the target p-phenylethynylphenol was synthesized.

<Synthesis of m-phenylethynylphenol (B)>
In a 100 ml three-necked flask containing a stirrer under a Dimroth tube and a nitrogen stream, 9.9845 g (0.058 mol) of 3-bromophenol and 17 ml of acetic anhydride were placed and reacted at 150 ° C. for 2 hours. The reaction was cooled to room temperature and distilled water was added. Extraction with diethyl ether, washing with distilled water, dehydration with anhydrous magnesium sulfate, and concentration with an evaporator gave 3-bromophenyl acetate.
A Dimroth tube, a 100 ml three-necked flask containing a stirring bar under a nitrogen stream, 12.432 g (0.58 mmol) of 3-bromophenyl acetate synthesized as described above, 7.8366 g (0.077 mmol) of ethynylbenzene, triphenyl Phosphine (0.1445 g, 0.501 mmol) and triethylamine (78 ml) were added, and the container was covered with aluminum foil to block light. A mixture of 0.0722 g (0.010 mmol) of palladium catalyst, 0.0291 g (0.153 mmol) of copper catalyst, and 5 ml of triethylamine prepared in a separate vessel was added thereto, and reacted at 120 ° C. for 12 hours.
The reaction was cooled to room temperature, filtered, extracted with diethyl ether, and the solvent triethylamine was removed with 0.1 N HCl. This solution was washed with distilled water, dehydrated with anhydrous magnesium sulfate, and concentrated with an evaporator to obtain 3-phenylethynyl acetate.
A solution containing 3-phenylethynyl acetate synthesized as described above, 9.6778 g (0.041 mmol) of potassium carbonate, and 70 ml of methanol were placed in a 100 ml three-necked flask containing a stir bar under a nitrogen stream under a Dimroth tube, and 90 ° C. The reaction was performed for 4 hours. Distilled water was added to the reaction solution, and methanol was removed with an evaporator. 0.1N HCl was added, extracted with diethyl ether, washed with distilled water, dehydrated with anhydrous magnesium sulfate, and subjected to an evaporator. Then, it refined by performing column chromatography with chloroform. Furthermore, it was recrystallized with hexane, dried under reduced pressure at 35 ° C. for 6 hours, and purified by sublimation.
As a result, 1.53 g (yield: 13.6%) of white powder was obtained. ¹ HNMR and ¹³ CNMR of the obtained compound were measured, and from the assignment of all signals, it was confirmed that the target m-phenylethynylphenol was synthesized.

<Synthesis of p-phenylethynylphenol-terminated polycarbonate (PC-A)>
In 1100 ml of 5 w / w% sodium hydroxide aqueous solution, 91.2 g (0.4 mol) of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”: manufactured by Nippon Steel Chemical Co., Ltd.) and hydro 0.1 g of sulfite was dissolved.
To this, 400 ml of methylene chloride was added and stirred. While maintaining the temperature at 15 ° C., 52 g of phosgene was blown at a rate of about 1 g / min.
After completion of phosgene blowing, 3.1 g (0.016 mol) of p-phenylethynylphenol (A) was added as a terminator and stirred vigorously to emulsify the reaction solution. After emulsification, 0.4 ml of triethylamine was added, The mixture was stirred at 20 to 27 ° C. for about 1 hour for polymerization.
After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the washing solution (aqueous phase) became 10 μS / cm or less. The obtained polymer solution was dropped into warm water maintained at 45 ° C., and the solvent was removed by evaporation to obtain a white powdery precipitate.
The obtained precipitate was filtered and dried at 105 ° C. for 24 hours to obtain a polymer powder.
The viscosity average molecular weight of this polymer was 23500. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, the polycarbonate resin having a carbonate bond (hereinafter " PC-A ”).

<Synthesis of m-phenylethynylphenol-terminated polycarbonate (PC-B)>
45.6 g (0.2 mol) of BPA and 0.05 g of hydrosulfite were dissolved in 550 ml of 5 w / w% sodium hydroxide aqueous solution.
To this, 200 ml of methylene chloride was added and stirred, and while maintaining the temperature at 15 ° C., 26 g of phosgene was blown in at a rate of about 1 g / min.
After completion of phosgene blowing, 1.52 g (0.008 mol) of the m-phenylethynylphenol (B) was added as a terminator and stirred vigorously to emulsify the reaction solution. After emulsification, 0.2 ml of triethylamine was added, The mixture was stirred at 20 to 27 ° C. for about 1 hour for polymerization.
After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the washing solution (aqueous phase) became 10 μS / cm or less. The obtained polymer solution was dropped into warm water maintained at 45 ° C., and the solvent was removed by evaporation to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 105 ° C. for 24 hours to obtain a polymer powder.
The viscosity average molecular weight of this polymer was 21,800. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, the polycarbonate resin having a carbonate bond (hereinafter " PC-B ").

<PC-C>
Product name “Iupilon (registered trademark) S-3000, hereinafter abbreviated as“ PC-C ””, viscosity average molecular weight: 21,300 (terminal structure is p-tert-butylphenol) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used.

<Synthesis of PC-D>
<Copolymerization of BPA with 1,2-bis (3-hydroxylphenyl) acetylene>
In 1100 ml of 5 w / w% aqueous sodium hydroxide solution, 87.6 g (0.384 mol) of BPA and 1,2-bis (3-hydroxyphenyl) acetylene (hereinafter abbreviated as “Ace”: Midori Chemical Co., Ltd.) 3.4 g ( 0.016 mol) and 0.1 g of hydrosulfite were dissolved.
To this, 400 ml of methylene chloride was added and stirred. While maintaining the temperature at 15 ° C., 52 g of phosgene was blown at a rate of about 1 g / min.
After the completion of phosgene blowing, 2.4 g (0.016 mol) of p-tert-butylphenol was added as a terminator and stirred vigorously to emulsify the reaction solution. After emulsification, 0.4 ml of triethylamine was added, and the temperature was 20 to 27 ° C. For about 1 hour to polymerize.
After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with water was repeated until the conductivity of the washing solution (aqueous phase) became 10 μS / cm or less. The obtained polymer solution was dropped into warm water maintained at 45 ° C., and the solvent was removed by evaporation to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 105 ° C. for 24 hours to obtain a polymer powder.
The viscosity average molecular weight of this polymer was 23900. The results obtained polymer was analyzed by infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, the polycarbonate resin having a carbonate bond (hereinafter " PC-D ").

<Other additives>
As the flame retardant, perfluorobutane sulfonic acid potassium salt, “trade name: Megafax F-114P” manufactured by Dainippon Chemical Ink Industries, Ltd. was used.
Tris (2,4-di-tert-butylphenyl) phosphite as a stabilizer: “ADEKA STAB 2112” manufactured by ADEKA, pentaerythritol tetrastearate as a release agent (1), manufactured by Cognis Japan “Product name: Roxyol VPG861” and octadecyl stearate, “Product name: Unistar M9766” manufactured by NOF Corporation were used as the release agent (2).

  The aromatic polycarbonate resin composition used in Example 1, Example 2, and Comparative Examples 1 to 3 was prepared by the following method. That is, after mixing each component with the content (addition ratio, mass%) shown in Table 1, using a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd .: 30C150), screw rotation speed 60 rpm, mixer temperature 260 ° C. The resin lump that was kneaded for 3 minutes under the conditions of the above, and the resin mass recovered after kneading was pulverized into pellets of 6 mmφ or less by a pulverizer (manufactured by Seishin Enterprise Co., Ltd .: Orient pulverizer VM-16), A sample of was obtained.

<Molding of Specimen 1>
In the test of transparency and hue, the obtained sample was dried at 120 ° C. for 5 hours, and then used on a tabletop injection molding machine (manufactured by HAAKE: MiniJet) with a cylinder temperature of 300 ° C., a mold temperature of 100 ° C., and residual heat. Injection molding was performed for 3 minutes under conditions of an injection pressure of 900 mb, and a plate-shaped molded product having a length of 50 mm, a width of 30 mm, and a thickness of 1.0 mm was molded as a test piece 1.

<Molding of Specimen 2>
In the flame retardancy test, the obtained sample was dried at 120 ° C. for 5 hours, and then used on a tabletop injection molding machine (manufactured by HAAKE: MiniJet) with a cylinder temperature of 300 ° C., a mold temperature of 100 ° C., and a preheating time. Injection molding was performed for 3 minutes under an injection pressure of 900 mb, and an Izod molded product was molded as a test piece 2. Thereafter, a combustion test was performed according to JIS K7201 using the molded sample, and the value of the oxygen index was measured. The larger the oxygen index, the harder it burns, and those exceeding 27 are classified as self-extinguishing plastics.

[Transparency evaluation]
Haze (haze value) (unit:%):
In accordance with JIS K-7105, the test piece 1 (1 mm thickness) was used as a test piece, and the haze value (unit: “%”) was measured with an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. The haze is a value used as a measure of the turbidity of the resin, and the smaller the numerical value, the higher the transparency. The results are shown in Table 1. In the table, “Haze” is used.

[Hue evaluation]
YI value:
Using the test piece 1 (thickness 1 mm) as a test piece, the YI value (Yellow Index) is measured by the transmission method with a SE2000 type spectrocolorimeter manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K-7105. did. A smaller YI value is preferable because the degree of yellowing of the resin is lower. The results are shown in Table 1. In the table, “YI” is used.

[Heat resistance evaluation]
Tg (glass transition temperature) (unit: ° C.):
For each of the resins PC-A to PC-D, Tg was measured with a DSC7020 high-sensitivity differential scanning calorimeter manufactured by SII Nanotechnology, in accordance with JIS K-7121. A larger value of Tg indicates better heat resistance, which is preferable. The results are shown in Table 1. In the table, “Tg” is used.

[Evaluation of flame retardancy]
The test piece 2 (Izod test piece) molded as described above was conditioned for 48 hours in a temperature-controlled room at a temperature of 23 ° C. and a relative humidity of 50%. The test was conducted in accordance with the above. In this test, those having a combustion oxygen index (LOI value) of 26 or more are considered to have flameproofing properties (self-extinguishing properties). In the table, “LOI” is used.

  The various measurement results obtained in Example 1, Example 2, and Comparative Examples 1 to 3 are shown in Table 1 below.

  As is clear from Table 1, in Examples 1 and 2, the LOI value is 40% or more, the Tg is kept at 146 ° C. or more, and the aromatics are excellent in heat resistance and flame retardancy. Polycarbonate was obtained. Also, the haze value was a low value of 1% or less, and the transparency was excellent.

  In Example 1 having a phenylethynylphenol end group at the para position, the YI value was as high as 8.3, and the hue was yellowish. On the other hand, in Example 2 having a phenylethynylphenol end group at the meta position, a molded product having a low YI value of 1.8 and excellent hue was obtained.

  On the other hand, in Comparative Examples 1 and 2 using a p-tert-butylphenol-terminated aromatic polycarbonate having no phenylethynylphenol end group, the LOI value remained at 38% even when a flame retardant metal salt was used, Flame retardancy was insufficient. In Comparative Example 3, an aromatic polycarbonate in which an ethynyl skeleton was introduced into the molecular chain was used with reference to Patent Document 5, but the LOI value was as high as 40%, but the haze value was 1. It was slightly higher as 01%, and the Tg was 132 ° C., which was nearly 20 ° C. lower than the p-tert-butylphenol terminated aromatic polycarbonate, resulting in poor heat resistance.

Claims (7)

(A) For 100 parts by mass of the aromatic polycarbonate resin having a terminal structure represented by the formula (A) and having a viscosity average molecular weight of 1 × 10 ^{4 to} 5 × 10 ⁴ , (b) an organic sulfonic acid metal salt An aromatic polycarbonate resin composition containing 0.005 parts by mass to 0.1 parts by mass.
Formula (A)

(In the formula (A), R ¹ is a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, a linear or branched alkenyl group having 2 to 9 carbon atoms, 9 linear or branched hydroxyalkyl groups, straight or branched hydroxyalkenyl groups having 2 to 9 carbon atoms, straight or branched haloalkyl groups having 1 to 9 carbon atoms, straight chain having 2 to 9 carbon atoms It is selected from a chain or branched haloalkenyl group and an optionally substituted aryl group having 6 to 12 carbon atoms, wherein R ^{6 to} R ⁹ each independently represents a hydrogen atom or a carbon atom having 1 to Selected from 9 alkyl groups and oxyalkyl groups having 1 to 9 carbon atoms.) The aromatic polycarbonate resin composition according to claim 1, wherein the formula (A) is represented by the following formula (B).
Formula (B)

(In Formula (B), R ^{6 to} R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms. R ¹⁷ to R ²¹ is independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms.) The aromatic polycarbonate resin composition according to claim 1, wherein the formula (A) is represented by the formula (C).
Formula (C)

(In formula (C), R ^{6 to} R ⁹ are each independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms. R ¹⁷ to R ²¹ is independently selected from a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, and an oxyalkyl group having 1 to 9 carbon atoms.) The aromatic polycarbonate resin according to any one of claims 1 to 3, wherein (b) the organic sulfonic acid metal salt is a fluoroalkanesulfonic acid alkali metal salt and / or a fluoroalkanesulfonic acid alkaline earth metal salt. Composition. The fragrance according to any one of claims 1 to 4, wherein at least one selected from a heat stabilizer, an antioxidant, a flame retardant aid, an ultraviolet absorber, a release agent and a colorant is blended. Group polycarbonate resin composition. The molded article shape | molded from the aromatic polycarbonate resin composition of any one of Claims 1-5. The molded article according to claim 6, wherein the haze value is 5% or less when the thickness is 1.0 mm.