JP2019127517A - Flame-retardant polycarbonate resin composition - Google Patents

Flame-retardant polycarbonate resin composition Download PDF

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JP2019127517A
JP2019127517A JP2018008859A JP2018008859A JP2019127517A JP 2019127517 A JP2019127517 A JP 2019127517A JP 2018008859 A JP2018008859 A JP 2018008859A JP 2018008859 A JP2018008859 A JP 2018008859A JP 2019127517 A JP2019127517 A JP 2019127517A
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JP7075225B2 (en
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博友 片野
Hirotomo Katano
博友 片野
麻里 藤本
Mari Fujimoto
麻里 藤本
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Daicel Polymer Ltd
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Abstract

To provide a polycarbonate resin composition capable of forming a molded product excellent in transparency and flame retardancy.SOLUTION: A flame-retardant polycarbonate resin composition comprises (A) a polycarbonate-polyorganosiloxane copolymer with a viscosity-average molecular weight of 10,000-40,000 which has a polycarbonate block including a repeating unit represented by the specified general formula (I) and a polyorganosiloxane block including a repeating unit represented by the specified general formula (II), (B) a flame retardant including 2,4,6-tris(2,4,6-trihalophenoxy)-1,3,5-triazine, and (C) a fluororesin. Based on 100 pts.mass of the component (A), the content of the component (B) is 4-15 pts.mass, and the content of the component (C) is 0.1-0.4 pts.mass.SELECTED DRAWING: None

Description

本発明は、透明で、難燃性が良い難燃性ポリカーボネート系樹脂組成物に関する。   The present invention relates to a flame retardant polycarbonate resin composition that is transparent and has good flame retardancy.

ガス器具用途や電子機器の外装などには、難燃性と耐薬品性が要求されており、難燃PBT/ABSのアロイからなる成形品に塗装をしたものが使用されている。
環境負荷の大きい塗装に代えて、樹脂にメタリック顔料などを添加して着色する要求があるが、前記のアロイでは透明性が劣るため、着色したときの発色性がよくない。
Flame retardancy and chemical resistance are required for gas appliance applications and exteriors of electronic devices, and those coated with a molded article made of a flame retardant PBT / ABS alloy are used.
There is a demand to add a metallic pigment or the like to a resin to color it instead of a paint having a large environmental load, but since the above-mentioned alloy is inferior in transparency, the coloring property when colored is not good.

特許文献1は、ポリカーボネート系樹脂と、2,4,6−トリス(2,4,6−トリハロフェノキシ)−1,3,5−トリアジンで構成されたハロゲン含有トリアジン化合物と、フッ素樹脂とで構成された難燃性透明樹脂組成物の発明が記載されており、難燃性、透明性、耐衝撃性に優れていることが記載されている。   Patent Document 1 is composed of a polycarbonate resin, a halogen-containing triazine compound composed of 2,4,6-tris (2,4,6-trihalophenoxy) -1,3,5-triazine, and a fluorine resin. The invention of the said flame-retardant transparent resin composition is described, and it is described that it is excellent in a flame retardance, transparency, and impact resistance.

特許第5118092号公報Patent No. 5118092 gazette

本発明は、透明で、難燃性の良い成形体が得られるポリカーボネート系樹脂組成物を提供することを課題とする。   An object of the present invention is to provide a polycarbonate resin composition from which a transparent and flame-retardant molded article can be obtained.

本発明は、(A)ポリカーボネート系樹脂、(B)2,4,6−トリス(2,4,6−トリハロフェノキシ)−1,3,5−トリアジンを含む難燃剤および(C)フッ素樹脂を含有しており、
(A)成分のポリカーボネート系樹脂が、下記一般式(I)で表される繰り返し単位を含むポリカーボネートブロックと、下記一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロックとを有する、粘度平均分子量が10,000〜40,000であるポリカーボネート−ポリオルガノシロキサン共重合体であり、
(A)成分100質量部に対する(B)成分の含有割合が4〜15質量部であり、(C)成分の含有割合が0.1〜0.4質量部である難燃性ポリカーボネート系樹脂組成物と、それから得られる成形体を提供する。
The present invention relates to a flame retardant comprising (A) polycarbonate resin, (B) 2,4,6-tris (2,4,6-trihalophenoxy) -1,3,5-triazine, and (C) a fluorine resin. Contains
The polycarbonate resin of component (A) has a polycarbonate block containing a repeating unit represented by the following general formula (I) and a polyorganosiloxane block containing a repeating unit represented by the following general formula (II) A polycarbonate-polyorganosiloxane copolymer having a viscosity average molecular weight of 10,000 to 40,000,
Flame retardant polycarbonate resin composition wherein the content of component (B) is 4 to 15 parts by mass and the content of component (C) is 0.1 to 0.4 parts by mass with respect to 100 parts by mass of component (A) And a molded article obtained therefrom.

Figure 2019127517
Figure 2019127517

(一般式(I)中、
1およびR2は、それぞれ独立にハロゲン原子、炭素数1〜6のアルキル基または炭素数1〜6のアルコキシ基を示し、
Xは単結合、炭素数1〜8のアルキレン基、炭素数2〜8のアルキリデン基、炭素数5〜15のシクロアルキレン基、炭素数5〜15のシクロアルキリデン基、フルオレンジイル基、炭素数7〜15のアリールアルキレン基、炭素数7〜15のアリールアルキリデン基、−S−、−SO−、−SO2−、−O−またはCO−を示し、
aおよびbは、それぞれ独立に0〜4の整数を示す。
一般式(II)中、
3およびR4は、それぞれ独立に水素原子、ハロゲン原子、炭素数1〜6のアルキル基、炭素数1〜6のアルコキシ基または炭素数6〜12のアリール基を示し、
平均繰り返し数nは、ポリオルガノシロキサンブロック中のシロキサン繰り返し単位の合計数を示す。)
(In general formula (I),
R 1 and R 2 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms,
X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenyl group, a carbon number 7-15 aryl alkylene groups, C7-15 aryl alkylidene groups, -S-, -SO-, -SO 2- , -O- or CO- is shown,
a and b each independently represent an integer of 0 to 4.
In general formula (II),
R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms,
The average repeat number n indicates the total number of siloxane repeat units in the polyorganosiloxane block. )

本発明のポリカーボネート系樹脂組成物から得られる成形体は、透明性と難燃性に優れている。   Molded articles obtained from the polycarbonate resin composition of the present invention are excellent in transparency and flame retardancy.

<ポリカーボネート系樹脂組成物>
(A)成分のポリカーボネート系樹脂は、一般式(I)で表される繰り返し単位を含むポリカーボネートブロックと、一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロックとを有するポリカーボネート−ポリオルガノシロキサン共重合体である。
<Polycarbonate resin composition>
The polycarbonate resin of component (A) is a polycarbonate-polycarbonate having a polycarbonate block containing a repeating unit represented by formula (I) and a polyorganosiloxane block containing a repeating unit represented by formula (II) It is an organosiloxane copolymer.

Figure 2019127517
Figure 2019127517

(一般式(I)中、
1およびR2は、それぞれ独立にハロゲン原子、炭素数1〜6のアルキル基または炭素数1〜6のアルコキシ基を示し、
Xは単結合、炭素数1〜8のアルキレン基、炭素数2〜8のアルキリデン基、炭素数5〜15のシクロアルキレン基、炭素数5〜15のシクロアルキリデン基、フルオレンジイル基、炭素数7〜15のアリールアルキレン基、炭素数7〜15のアリールアルキリデン基、−S−、−SO−、−SO2−、−O−またはCO−を示し、
aおよびbは、それぞれ独立に0〜4の整数を示す。
一般式(II)中、
3およびR4は、それぞれ独立に水素原子、ハロゲン原子、炭素数1〜6のアルキル基、炭素数1〜6のアルコキシ基または炭素数6〜12のアリール基を示し、
平均繰り返し数nは、ポリオルガノシロキサンブロック中のシロキサン繰り返し単位の合計数を示す。)
(In general formula (I),
R 1 and R 2 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms,
X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenyl group, a carbon number 7-15 aryl alkylene groups, C7-15 aryl alkylidene groups, -S-, -SO-, -SO 2- , -O- or CO- is shown,
a and b each independently represent an integer of 0 to 4.
In general formula (II),
R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms,
The average repeat number n indicates the total number of siloxane repeat units in the polyorganosiloxane block. )

(A)成分は、粘度平均分子量が10,000〜40,000であり、好ましくは10,000〜30,000である。
一般式(I)で表される繰り返し単位を含むポリカーボネートブロックと一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロックは、(A)成分が上記粘度範囲になるようにそれぞれの繰り返し単位数が調整される。
粘度平均分子量(Mv)は、ウベローデ型粘度計を用いて、20℃における塩化メチレン溶液の粘度を測定し、これより極限粘度[η]を求め、次式にて算出することができる(特開2008-202012号公報参照)。
[η]=1.23×10-5Mv0.83
The component (A) has a viscosity average molecular weight of 10,000 to 40,000, preferably 10,000 to 30,000.
The polycarbonate block containing the repeating unit represented by the general formula (I) and the polyorganosiloxane block containing the repeating unit represented by the general formula (II) have their respective repeating units so that the component (A) has the above viscosity range. The number of units is adjusted.
The viscosity average molecular weight (Mv) can be calculated by the following equation by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, and determining the intrinsic viscosity [η] 2008-202012 publication).
[Η] = 1.23 × 10 −5 Mv0.83

(A)成分のポリカーボネート−ポリオルガノシロキサン共重合体は、一分子中のSi量が1〜10質量%の範囲であるものが好ましい。   The polycarbonate-polyorganosiloxane copolymer of the component (A) is preferably one in which the amount of Si in one molecule is in the range of 1 to 10% by mass.

(B)成分は、2,4,6−トリス(2,4,6−トリハロフェノキシ)−1,3,5−トリアジン(以下「ハロゲン含有トリアジン化合物」という)を含む難燃剤である。
前記ハロゲン含有トリアジン化合物は、ハロゲン原子が臭素原子であるものが好ましい。
(B)成分は、前記ハロゲン含有トリアジン化合物のみからなるものでもよいし、前記ハロゲン含有トリアジン化合物と公知の他の難燃剤を併用したものでもよい。
前記ハロゲン含有トリアジン化合物と公知の他の難燃剤を併用したときは、合計量中の他の難燃剤の含有量は10質量%以下が好ましく、5質量%以下が好ましく、3質量%以下がより好ましい。
Component (B) is a flame retardant containing 2,4,6-tris (2,4,6-trihalophenoxy) -1,3,5-triazine (hereinafter referred to as "halogen-containing triazine compound").
The halogen-containing triazine compound is preferably one in which a halogen atom is a bromine atom.
The component (B) may consist only of the halogen-containing triazine compound, or may be a combination of the halogen-containing triazine compound and another known flame retardant.
When the halogen-containing triazine compound and other known flame retardants are used in combination, the content of the other flame retardant in the total amount is preferably 10% by mass or less, preferably 5% by mass or less, and 3% by mass or less preferable.

(C)成分はフッ素樹脂である。
(C)成分のフッ素樹脂の平均粒径は0.05〜1μmが好ましく、0.1〜0.5μmがより好ましく、0.1〜0.3μmがさらに好ましい。
平均粒径は、光散乱法により測定する。
Component (C) is a fluororesin.
The average particle diameter of the fluorine resin of the component (C) is preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm, and still more preferably 0.1 to 0.3 μm.
The average particle diameter is measured by a light scattering method.

(A)、(B)、(C)成分の含有割合は、
(A)成分100質量部に対して(B)成分は4〜15質量部、好ましくは4〜12質量部であり、
(A)成分100質量部に対して(C)成分は0.1〜0.4質量部、好ましくは0.1〜0.3質量部である。
The content ratio of the components (A), (B), (C) is
Component (B) is 4 to 15 parts by mass, preferably 4 to 12 parts by mass, per 100 parts by mass of component (A),
Component (C) is used in an amount of 0.1 to 0.4 parts by mass, preferably 0.1 to 0.3 parts by mass, per 100 parts by mass of component (A).

本発明の組成物は、必要に応じて、特開2016−153442号公報、特開2016−153443号公報に記載の炭素数15〜19の飽和アルコールと炭素数16〜22の飽和脂肪酸からなるエステル化合物、リン系安定剤などの安定剤を含有することができる。   The composition of the present invention is an ester comprising a saturated alcohol having 15 to 19 carbon atoms and a saturated fatty acid having 16 to 22 carbon atoms, as described in JP-A-2016-153442 and JP-A-2016-153443, as necessary. The compound may contain a stabilizer such as a phosphorus-based stabilizer.

本発明の組成物は、用途に応じて、慣用の添加剤、例えば、他の安定化剤(例えば、酸化防止剤、紫外線吸収剤、耐光安定剤など)、着色剤(染料、顔料など)、帯電防止剤、架橋剤、核剤、カップリング剤、分散剤、消泡剤、流動化剤、抗菌剤、防腐剤、粘度調整剤、増粘剤などを含んでいてもよい。   The composition of the present invention may contain conventional additives such as other stabilizers (eg, antioxidants, UV absorbers, light stabilizers, etc.), colorants (dyes, pigments etc.), depending on the application. Antistatic agents, crosslinking agents, nucleating agents, coupling agents, dispersing agents, antifoaming agents, fluidizers, antibacterial agents, preservatives, viscosity modifiers, thickeners and the like may be included.

本発明の組成物は、例えば、各成分をタンブラーミキサー、ヘンシェルミキサー、リボンミキサー、ニーダーなどの混合機を用いて乾式または湿式で混合して調製してもよい。
さらに、前記混合機で予備混合した後、一軸または二軸押出機などの押出機で混練してペレットに調製する方法、加熱ロールやバンバリーミキサーなどの混練機で溶融混練して調製する方法を適用することができる。
The composition of the present invention may be prepared, for example, by mixing the respective components dry or wet using a mixer such as a tumbler mixer, a Henschel mixer, a ribbon mixer, a kneader or the like.
Furthermore, after pre-mixing with the mixer, a method of preparing into pellets by kneading with an extruder such as a single-screw or twin-screw extruder, or a method of preparing by melt-kneading with a mixer such as a heating roll or a Banbury mixer is applied. can do.

<難燃性ポリカーボネート系樹脂組成物の成形体>
本発明の成形体は、上記した難燃性ポリカーボネート系樹脂組成物を使用して、射出成形、押出成形、真空成形、異型成形、発泡成形、インジェクションプレス、プレス成形、ブロー成形、ガス注入成形などによって、用途に応じた所望形状の成形体にすることができる。
本発明の成形体は、下記の(i)〜(iii)の要件を全て満たすものが好ましい。
(i)試験片の厚み3mmで測定したとき、ASTMD1003−00に準拠した全光線透過率が50%以上であること。
(ii)試験片の厚み1.5mmで測定したとき、UL94燃焼性試験に準拠した難燃性がV−0であること。
(iii)ISO179に準拠した耐衝撃性(シャルピー衝撃強度)が5kJ/cm2以上であること。
<Molded product of flame retardant polycarbonate resin composition>
The molded article of the present invention is produced by injection molding, extrusion molding, vacuum molding, profile molding, foam molding, injection press, press molding, blow molding, gas injection molding, etc., using the above-mentioned flame retardant polycarbonate resin composition. Thus, a molded body having a desired shape according to the application can be obtained.
The molded article of the present invention preferably satisfies all of the following requirements (i) to (iii).
(I) that the total light transmittance according to ASTM D 1003-00 is 50% or more when measured with a thickness of 3 mm of the test piece.
(Ii) The flame retardancy according to the UL 94 flammability test is V-0 when measured with a thickness of 1.5 mm of the test piece.
(Iii) The impact resistance (Charpy impact strength) in accordance with ISO 179 is 5 kJ / cm 2 or more.

<使用成分>
(A)成分
PDMS−PC:ポリカーボネート中にシロキサン分子を共重合したシロキサンポリカーボネートコポリマー(出光興産株式会社製,タフロン ネオ RC1760)(粘度平均分子量17000,Si量約6質量%)
(B)成分
FR1:2,4,6−トリス(2,4,6−トリブロモフェノキシ)−1,3,5−トリアジン(商品名「ピロガードSR245」、第一工業製薬(株)製)
比較(B)成分
FR2:テトラブロモビスフェノールAジグリシジルエーテルとブロム化ビスフェノール付加物(商品名「プラサームEP16」、大日本インキ化学工業(株)製)
FR3:1,2−ビス(2,3,4,5,6−ペンタブロモフェニルエタン)(商品名「Saytex8010」、アルベマール(株)製)
(C)成分
フッ素樹脂:ポリテトラフルオロエチレン(商品名「ポリフロンPTFED210C」、ダイキン工業(株)製、フッ素化ポリエチレン含有量60質量%、平均粒径0.22μm)
(他の添加剤)
添加剤1:離型剤(商品名「リケマールSL800」、理研ビタミン(株)製、主成分:ステアリルステアレート)
添加剤2:フェノール系酸化防止剤(商品名「イルガノックス1010」、チバジャパン製、主成分:ペンタエリスリトールテトラキス[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート])
添加剤3:イオウ系酸化防止剤(商品名「スミライザーTPS」、住友化学工業(株)製、主成分:ジステアリル−3,3’−チオジプロピオネート)
<Use ingredients>
(A) Component PDMS-PC: Siloxane polycarbonate copolymer obtained by copolymerizing siloxane molecule in polycarbonate (Tareflon manufactured by Idemitsu Kosan Co., Ltd. Neo RC 1760) (viscosity average molecular weight 17000, Si content about 6 mass%)
(B) Component FR 1: 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine (trade name "Pyrogard SR245", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Comparison (B) Component FR2: Tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct (trade name "Prasame EP 16", manufactured by Dainippon Ink and Chemicals, Inc.)
FR3: 1,2-bis (2,3,4,5,6-pentabromophenylethane) (trade name "Saytex 8010", manufactured by Albemarle Corporation)
(C) Component Fluorine resin: polytetrafluoroethylene (trade name "Polyflon PTFE D 210C", manufactured by Daikin Industries, Ltd., fluorinated polyethylene content 60 mass%, average particle diameter 0.22 μm)
(Other additives)
Additive 1: mold release agent (trade name "Rikemar SL 800", manufactured by Riken Vitamin Co., Ltd., main component: stearyl stearate)
Additive 2: Phenolic antioxidant (trade name "Irganox 1010", manufactured by Ciba Japan, main component: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate])
Additive 3: Sulfur-based antioxidant (trade name "Sumilyzer TPS", manufactured by Sumitomo Chemical Co., Ltd., Main component: Distearyl-3,3'-thiodipropionate)

<各特性の評価方法>
[透明性]
射出成形法により作製した厚さ3mmの平板につき、ASTMD1003−00に準拠し、全光線透過率(%)を測定して、評価した。
[難燃性]
米国アンダーライターラボラトリーズ発行のUL94に準拠した方法で、1.5mmの厚みのサンプルにつき燃焼試験を実施した。
[耐衝撃性]
ISO179に準拠した方法で、シャルピー衝撃値(kJ/cm2)を測定し、評価した。
<Evaluation method of each characteristic>
[transparency]
With respect to a flat plate of 3 mm in thickness prepared by the injection molding method, the total light transmittance (%) was measured and evaluated in accordance with ASTM D1003-00.
[Flame retardance]
A burn test was performed on a 1.5 mm thick sample in accordance with UL 94 issued by Underwriters Laboratories, USA.
[Shock resistance]
The Charpy impact value (kJ / cm 2 ) was measured and evaluated by a method according to ISO 179.

実施例および比較例
表1に示す配合(質量%、質量部)で各成分を配合し、ヘンシェルミキサーで混合した。
その後、前記混合物を押出機に供給して250℃で溶融混練し、ペレットを得た。
このペレットを250℃で射出成形して各試験片を作製し、各測定を実施した。結果を表1に示す。
Examples and Comparative Examples Each component was compounded in the composition (mass%, mass part) shown in Table 1 and mixed with a Henschel mixer.
Thereafter, the mixture was supplied to an extruder and melt-kneaded at 250 ° C. to obtain pellets.
The pellets were injection molded at 250 ° C. to prepare test pieces, and each measurement was performed. The results are shown in Table 1.

(射出成形条件)
成形機:三菱重工(株)社製 100MS-II(型締力100t)、シリンダー径36mm
成形温度:250℃、金型温度:60℃
(Injection molding conditions)
Molding machine: Mitsubishi Heavy Industries, Ltd. 100MS-II (clamping force 100t), cylinder diameter 36mm
Molding temperature: 250 ° C, mold temperature: 60 ° C

Figure 2019127517
Figure 2019127517

実施例に示すように、本発明の構成要件を満足するものについては、要求性能を満たしていた。
一方、比較例に示すように、本発明の構成要件を満足しないものについては、以下のような欠点を有していた。
比較例1は、(B)成分の含有量が少ないため、V−0に適合しなかった。
比較例2は、(B)成分の含有量が多いため、シャルピー衝撃値が低い値となった。
比較例3は、(C)成分の含有量が少ないため、V−0に適合しなかった。
比較例4は、(C)成分の含有量が多いため、全光線透過率が不良となった。
比較例5〜6は、難燃剤として比較用(B)成分を使用しているため、全光透過率が不良となった。
As shown in the examples, the required performance was satisfied for those satisfying the constituent requirements of the present invention.
On the other hand, as shown in the comparative example, those which do not satisfy the constituent requirements of the present invention have the following disadvantages.
Comparative Example 1 did not conform to V-0 because the content of the component (B) was small.
In Comparative Example 2, since the content of the component (B) was large, the Charpy impact value was a low value.
Comparative Example 3 did not conform to V-0 because the content of the component (C) was low.
In Comparative Example 4, the total light transmittance was poor because the content of the component (C) was large.
In Comparative Examples 5 to 6, the component for comparison (B) was used as the flame retardant, so that the total light transmittance was poor.

本発明のポリカーボネート系樹脂組成物から得られる成形体は、耐熱性や耐薬品性(耐油性)が要求される用途に適しており、例えば、ガス器具用途や電子機器の外装用途などに利用することができる。   The molded product obtained from the polycarbonate resin composition of the present invention is suitable for applications requiring heat resistance and chemical resistance (oil resistance), and is used, for example, for gas appliances and exterior applications of electronic devices. be able to.

Claims (5)

(A)ポリカーボネート系樹脂、(B)2,4,6−トリス(2,4,6−トリハロフェノキシ)−1,3,5−トリアジンを含む難燃剤および(C)フッ素樹脂を含有しており、
(A)成分のポリカーボネート系樹脂が、下記一般式(I)で表される繰り返し単位を含むポリカーボネートブロックと、下記一般式(II)で表される繰り返し単位を含むポリオルガノシロキサンブロックとを有する、粘度平均分子量が10,000〜40,000であるポリカーボネート−ポリオルガノシロキサン共重合体であり、
(A)成分100質量部に対する(B)成分の含有割合が4〜15質量部であり、(C)成分の含有割合が0.1〜0.4質量部である難燃性ポリカーボネート系樹脂組成物。
Figure 2019127517
(一般式(I)中、
1およびR2は、それぞれ独立にハロゲン原子、炭素数1〜6のアルキル基または炭素数1〜6のアルコキシ基を示し、
Xは単結合、炭素数1〜8のアルキレン基、炭素数2〜8のアルキリデン基、炭素数5〜15のシクロアルキレン基、炭素数5〜15のシクロアルキリデン基、フルオレンジイル基、炭素数7〜15のアリールアルキレン基、炭素数7〜15のアリールアルキリデン基、−S−、−SO−、−SO2−、−O−またはCO−を示し、
aおよびbは、それぞれ独立に0〜4の整数を示す。
一般式(II)中、
3およびR4は、それぞれ独立に水素原子、ハロゲン原子、炭素数1〜6のアルキル基、炭素数1〜6のアルコキシ基または炭素数6〜12のアリール基を示し、
平均繰り返し数nは、ポリオルガノシロキサンブロック中のシロキサン繰り返し単位の合計数を示す。)
(A) A polycarbonate resin, (B) a flame retardant containing 2,4,6-tris (2,4,6-trihalophenoxy) -1,3,5-triazine, and (C) a fluororesin ,
The polycarbonate resin of component (A) has a polycarbonate block containing a repeating unit represented by the following general formula (I) and a polyorganosiloxane block containing a repeating unit represented by the following general formula (II) A polycarbonate-polyorganosiloxane copolymer having a viscosity average molecular weight of 10,000 to 40,000,
Flame retardant polycarbonate resin composition wherein the content of component (B) is 4 to 15 parts by mass and the content of component (C) is 0.1 to 0.4 parts by mass with respect to 100 parts by mass of component (A) object.
Figure 2019127517
(In general formula (I),
R 1 and R 2 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms,
X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenyl group, a carbon number 7-15 aryl alkylene groups, C7-15 aryl alkylidene groups, -S-, -SO-, -SO 2- , -O- or CO- is shown,
a and b respectively independently show the integer of 0-4.
In general formula (II),
R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms,
The average repeat number n indicates the total number of siloxane repeat units in the polyorganosiloxane block. )
(A)成分100質量部に対する(B)成分の含有割合が4〜12質量部、(C)成分の含有割合が0.1〜0.3質量部である、請求項1記載の難燃性ポリカーボネート系樹脂組成物。   The flame retardancy according to claim 1, wherein the content of the component (B) is 4 to 12 parts by mass and the content of the component (C) is 0.1 to 0.3 parts by mass with respect to 100 parts by mass of the component (A). Polycarbonate resin composition. (C)成分の平均粒径が0.05〜1μmである請求項1または2記載の難燃性ポリカーボネート系樹脂組成物。   The flame-retardant polycarbonate resin composition according to claim 1 or 2, wherein the average particle diameter of the component (C) is 0.05 to 1 μm. (i)試験片の厚み3mmで測定したとき、ASTMD1003−00に準拠した全光線透過率が50%以上であり、
(ii)試験片の厚み1.5mmで測定したとき、UL94燃焼性試験に準拠した難燃性がV−0であり、
(iii)ISO179に準拠した耐衝撃性が5kJ/cm2以上である請求項1〜3のいずれか1項に記載の難燃性ポリカーボネート系樹脂組成物。
(I) When measured with a thickness of 3 mm of the test piece, the total light transmittance according to ASTM D 1003-00 is 50% or more,
(Ii) The flame retardancy according to the UL 94 flammability test is V-0 when measured with a thickness of 1.5 mm of the test piece,
(Iii) The flame retardant polycarbonate resin composition according to any one of claims 1 to 3, which has an impact resistance of 5 kJ / cm 2 or more according to ISO 179.
請求項1〜4のいずれか1項に記載の難燃性ポリカーボネート系樹脂組成物からなる成形体。   The molded object which consists of a flame-retardant polycarbonate-type resin composition of any one of Claims 1-4.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03243656A (en) * 1990-02-21 1991-10-30 Idemitsu Petrochem Co Ltd Glass fiber reinforced polycarbonate resin composition
JP5118092B2 (en) * 2009-03-30 2013-01-16 ダイセルポリマー株式会社 Flame retardant transparent polycarbonate resin composition
WO2013051557A1 (en) * 2011-10-03 2013-04-11 出光興産株式会社 Polycarbonate resin composition
JP2015108117A (en) * 2013-10-21 2015-06-11 三菱エンジニアリングプラスチックス株式会社 Thermally conductive polycarbonate resin composition and molded product
WO2016159025A1 (en) * 2015-03-30 2016-10-06 出光興産株式会社 Polycarbonate resin composition and molded body of same
WO2016159024A1 (en) * 2015-03-30 2016-10-06 出光興産株式会社 Polycarbonate resin composition and molded body of same
WO2016203916A1 (en) * 2015-06-17 2016-12-22 出光興産株式会社 Preparation method for polycarbonate resin composition
WO2016203917A1 (en) * 2015-06-17 2016-12-22 出光興産株式会社 Polycarbonate resin composition and molded product thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03243656A (en) * 1990-02-21 1991-10-30 Idemitsu Petrochem Co Ltd Glass fiber reinforced polycarbonate resin composition
JP5118092B2 (en) * 2009-03-30 2013-01-16 ダイセルポリマー株式会社 Flame retardant transparent polycarbonate resin composition
WO2013051557A1 (en) * 2011-10-03 2013-04-11 出光興産株式会社 Polycarbonate resin composition
JP2015108117A (en) * 2013-10-21 2015-06-11 三菱エンジニアリングプラスチックス株式会社 Thermally conductive polycarbonate resin composition and molded product
WO2016159025A1 (en) * 2015-03-30 2016-10-06 出光興産株式会社 Polycarbonate resin composition and molded body of same
WO2016159024A1 (en) * 2015-03-30 2016-10-06 出光興産株式会社 Polycarbonate resin composition and molded body of same
WO2016203916A1 (en) * 2015-06-17 2016-12-22 出光興産株式会社 Preparation method for polycarbonate resin composition
WO2016203917A1 (en) * 2015-06-17 2016-12-22 出光興産株式会社 Polycarbonate resin composition and molded product thereof

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