JP3613911B2 - Flame retardant resin composition - Google Patents

Description

【００２５】
上記一般式(I)において、Ｒ^ａ〜Ｒ^ｃの炭化水素基の炭素原子数は好ましくは２〜１６、特に好ましくは６〜１０である。炭化水素基の例としてはアルキル基、シクロアルキル基、アラルキル基、置換されていないアリール基、置換されたアリール基があり、置換されたアリール基としてはアルカリール基、シクロアルカリール基、アリール置換アルカリール基及びアリール置換アリール基が挙げられる。アルキル基の例としてはメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、オクチル、ノニル、デシル、ウンデシル、ドデシル、ネオペンチル、３，５，５−トリメチルヘキシル、３−メチルヘキシル、２−エチルヘキシル及び２，５，５−トリメチルヘキシルが挙げられる。シクロアルキル基の例としてはシクロヘキシルが挙げられる。アラルキル基の例としてはベンジル及びフェネチルが挙げられる。置換されていないアリール基の例としてはフェニル及びナフチルが挙げられる。アルカリール基の例としてはｏ−，ｐ−及びｍ−トリル、２，６−及び２，４−ジメチルフェニル、トリメチルフェニル、ｏ−，ｐ−及びｍ−イソプロピルフェニル、ノニルフェニル、ｐ−ｔ−ブチルフェニル、２，４−ジイソプロピルフェニル及びトリイソプロピルフェニルが挙げられる。シクロアルカリール基の例としてはｏ−シクロヘキシルフェニルが挙げられる。アリール置換アルカリール基の例としてはｐ−ベンジルフェニル及びｐ−フェネチルフェニルが挙げられる。アリール置換アリール基の例としてはジフェニルが挙げられる。
【００２６】
上記一般式(I)において、Ｒ^ａ，Ｒ^ｂ及びＲ^ｃはアリール基又はアルカリール基であることが好ましく、特に、フェニル、ｏ−，ｐ−及びｍ−トリル、２，６−ジメチルフェニル及び２，４−ジイソプロピルフェニルであることが好ましい。
【００２７】
本発明で用いるリン酸エステル系難燃剤（Ｄ）の具体例としては次のようなものが挙げられる。
【００２８】
トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、クレジルフェニルホスフェート、オクチルジフェニルホスフェート、ジイソプロピルフェニルホスフェート、トリス（クロロエチル）ホスフェート、トリス（ジクロロプロピル）ホスフェート、トリス（クロロプロピル）ホスフェート、ビス（２，３−ジブロモプロピル）−２，３−ジクロロプロピルホスフェート、トリス（２，３−ジブロモプロピル）ホスフェート及びビス（クロロプロピル）モノオクチルホスフェート、置換基としてアルコキシ例えばメトキシ、エトキシ及びプロポキシ、又は好ましくは（置換）フェノキシ例えばフェノキシ、メチル（置換）フェノキシを有するビスフェノールＡビスホスフェート、ヒドロキノンビスホスフェート、レゾルシンビスホスフェート、トリオキシベンゼントリホスフェート等。好ましくはトリフェニルホスフェート及び各種ビスホスフェートが挙げられる。
【００２９】
本発明で用いるポリオルガノシロキサングラフト共重合体（Ｅ）は、下記一般式(II)で表わされるポリオルガノシロキサンに、ポリエチレン、ポリプロピレン、エチレン−メチルメタクリレート共重合体、エチレン−酢酸ビニル共重合体から選ばれるポリオレフィン系熱可塑性樹脂をグラフト共重合して得られるものである。
【００３０】
【化３】

【００３１】
上記(II)式中、Ｒ^１〜Ｒ^８の具体例としては、芳香族炭化水素基の場合には、フェニル、キシリル、トリル等のアリール基；クロロフェニル等のハロゲン化アリール基；フェニルエチル、ベンジルのアラルキル基が挙げられ、脂肪族炭化水素基の場合には、メチル、エチル、プロピル等のアルキル基；ビニル、プロペニル、ブテニル等のアルケニル基；シアノエチル、シアノブチル等のシアノアルキル基；クロロブチル等のハロアルキル基等が挙げられ、脂環式炭化水素基の場合にはシクロヘキシル等が挙げられる。Ｒ^１〜Ｒ^８は、すべて同じであっても、互いに異なっていてもよい。Ｒ^１〜Ｒ^８は好ましくはメチル、フェニル及びビニルから選択される。
【００３２】
上記（II）式で示されるポリオルガノシロキサンは、その一部に、反応性の官能基、例えばエポキシ基、アミノ基、カルボン酸基、カルボン酸エステル基、メルカプト基、水酸基等を付加して用いてもよい。また、不飽和基を付加したビニル基含有ポリオルガノシロキサンを用いてもよい。
【００３３】
ポリオルガノシロキサングラフト共重合体（Ｅ）は、上記ポリオルガノシロキサン３０〜７０重量％と前記ポリオレフィン系熱可塑性樹脂７０〜３０重量％とを、有機化酸化物の存在下又は不存在下で混練することにより製造することができる。
【００３４】
ポリオルガノシロキサングラフト共重合体（Ｅ）としては、具体的には、前記(II)式においてＲ^１〜Ｒ^８の一部が不飽和ビニル基を含有したビニル官能基含有ポリオルガノシロキサン６０重量％と、エチレン−酢酸ビニル共重合体４０重量％とをグラフト共重合して得られたポリオルガノシロキサングラフト共重合体「ＳＰ−１１０」（ダウコーニングアジア社製 商品名）を用いることができる。
【００３５】
本発明では、リン酸エステル系難燃剤（Ｄ）及びポリオルガノシロキサングラフト共重合体（Ｅ）を併用することによる優れた相乗効果で優れた難燃化効果を得ると共に、ポリオルガノシロキサングラフト共重合体（Ｅ）により、良好な耐衝撃性、摺動性等の特性が得られ、また、耐熱性も良好なものとなる。このような各成分の相乗効果を基礎樹脂組成物の物性を損なうことなく得るために、本発明においては、基礎樹脂組成物１００重量部に対して、
リン酸エステル系難燃剤（Ｄ）：５〜２０重量部、好ましくは９〜１５重量部
ポリオルガノシロキサングラフト共重合体（Ｅ）：０．１〜５重量部、好ましくは０．５〜４重量部
を配合する。
【００３６】
ポリオルガノシロキサングラフト共重合体（Ｅ）が０．１重量部未満ではＵＬ９４規格Ｖ−２以上の難燃性が得られず、５重量部を超えると剛性が低下し、また、難燃性も悪くなる。
【００３７】
なお、本発明においては、更に、滴下防止剤として、テトラフルオロエチレンを主成分として重合して得られるフッ化炭化水素、例えばポリテトラフルオロエチレンを配合しても良い。この場合、ポリテトラフルオロエチレンの配合量は、基礎樹脂組成物１００重量部に対して０．０１〜２重量部、特に０．０５〜１．０重量部とするのが好ましい。
【００３８】
また、本発明の難燃性樹脂組成物には、上記の諸成分の他に、その物性を損なわない限りにおいて、樹脂組成物の製造時（混合時）、成形時に慣用の他の添加剤、例えば顔料、染料、充填剤（カーボンブラック、シリカ、酸化チタン等）、耐熱剤、酸化劣化防止剤、耐候剤、滑剤、離型剤、可塑剤、帯電防止剤等を添加することができる。
【００３９】
このような本発明の難燃性樹脂組成物を製造する方法には特に制限はなく、通常行われている方法及び装置を使用して製造することができる。一般的に使用されている方法としては溶融混合法があり、その装置の例としては押出機、バンバリーミキサー、ローラー、ニーダー等を挙げることができる。この製造は回分式又は連続式のいずれでもよく、各成分の混合順序にも特に限定はなく、全ての成分が完全に混ぜ合わされればよい。
【００４０】
【実施例】
以下に実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。
【００４１】
なお、実施例及び比較例で用いた芳香族ポリカーボネート樹脂（Ａ）、ゴム含有グラフト共重合体（Ｂ）、硬質共重合体（Ｃ）、リン酸エステル系難燃剤（Ｄ）及びポリオルガノシロキサングラフト共重合体（Ｅ）は下記の通りである：
（Ａ）芳香族ポリカーボネート樹脂：
パンライトＬ−１２５０（帝人化成（株）製））（２，２−ビス（４−ヒドロキシ フェニル）プロパンとホスゲンとから得られた芳香族ポリカーボネート樹脂
（Ｂ）ゴム含有グラフト共重合体：
グラフト共重合体Ｂ−１：乳化重合によるＡＢＳ樹脂
ポリブタジエン ５０重量％
スチレン ３５重量％
アクリロニトリル １５重量％
グラフト共重合体Ｂ−２：乳化重合によるＡＡＳ樹脂
アクリル酸エステルゴム ５０重量％
スチレン ３５重量％
アクリロニトリル １５重量％
（Ｃ）硬質共重合体：懸濁重合によるＳＡＮ樹脂
スチレン ７４重量％
アクリロニトリル ２６重量％
（Ｄ）リン酸エステル系難燃剤：
トリフェニルホスフェート（ＴＰＰ）
商品名「ＣＲ７３３Ｓ」大八化学（株）製（下記構造式の芳香族リン酸オリゴマー （ただし、式中ｎは１以上の整数））
【００４２】
【化４】

（Ｅ）ポリオルガノシロキサングラフト共重合体：
商品名「ＳＰ−１１０」ダウコーニングアジア社製
【００４３】
実施例１〜８，比較例１〜５
表２，３に示す配合割合にて各成分をヘンシェルミキサーで混合し、押出機で混練ペレット化した。得られたペレットを２６０℃で射出成形して成形品を得た。得られた成形品について下記試験方法で諸物性と難燃性の評価を行い、結果を表２，３に示した。
【００４４】
(1) アイゾット衝撃強度（Ｋｇ・ｃｍ／ｃｍ）：ＡＳＴＭ Ｄ ２５６に従って、厚み１／８インチ、ノッチ付きで測定した。
(2) 曲げ弾性率（Ｋｇ／ｃｍ^２）：ＡＳＴＭ Ｄ ７９０に準拠して測定した。
(3) 熱変形温度（℃）：ＡＳＴＭ Ｄ ６４８−５６に準拠して測定した。
(4) 動摩擦係数（−）：ＪＩＳＫ７２１８−Ａ法に準拠して測定した。
試験条件
相手材料：ポリオキンメチレン
試験荷重：１．５ｋｇ
試験速度：１００ｍｍ／ｓｅｃ
(5) 難燃性：ＵＬ９４規格の試験方法に従って、厚み１／１０，１／１２、１／１６インチで試験を実施した。供試材料を試料（Ｖの評価の試料数：５，ＨＢの評価の試料数：３）の試験結果に基づいてＵＬ−９４ Ｖ−０、Ｖ−１，Ｖ−２及びＨＢのいずれかの等級に評価した。各等級の基準の概略は次の通りである。
【００４５】
【表１】

【００４６】
【表２】

【００４７】
【表３】

【００４８】
表２，３より明らかなように、本発明の難燃性樹脂組成物（実施例１〜８）では衝撃強度、曲げ弾性率、熱変形温度及び摺動性の諸物性において良好な特性を示し、１／１０”、１／１２”、１／１６”の全ての厚みの試験片において優れた難燃特性を示した。
【００４９】
これに対して、本発明の範囲外の樹脂組成物（比較例１〜５）では、難燃性及び／又は他の物性に劣る。特に、比較例１，５のポリオルガノシロキサングラフト共重合体が配合されてないもの、及びポリオルガノシロキサングラフト共重合体の配合量が多い比較例２，４では、曲げ弾性率が低くまた難燃特性が悪い。また、比較例３のポリオルガノシロキサングラフト共重合体の代りにポリメチルフェニルシリコーンを配合したものは十分な難燃特性が得られなかった。
【００５０】
【発明の効果】
以上詳述した通り、本発明の難燃性樹脂組成物は、耐衝撃性、剛性等の強度特性及び難燃性、摺動性、流動性、熱安定性等に優れ、特に耐衝撃性、摺動性及び難燃性に非常に優れていることから、薄肉での成形品においても、その特性を十分に発揮するため、ＯＡ機器のハウジング材料やエンクロージャー材料等における要望にも十分対応でき、工業的に非常に有用である。また、難燃剤として有機ハロゲン化合物を使用していないことから、環境問題の観点からも非常に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a flame retardant resin composition, and more particularly to a flame retardant resin composition having excellent flame retardancy, and having good impact resistance and slidability.
[0002]
[Prior art]
A resin composition containing an aromatic polycarbonate resin and an ABS resin has excellent strength properties, impact resistance, heat resistance, dimensional stability, etc., and is therefore widely used as a housing material and enclosure material for OA equipment. It has been.
[0003]
However, since this resin composition lacks flame retardancy, various improvements have been made for the purpose of improving flame retardancy. For example, Japanese Patent Application Laid-Open No. 64-22958 discloses a method for imparting flame retardancy by adding an organic halogen compound as a flame retardant and antimony trioxide as a flame retardant aid. However, the addition of such an organic halogen compound lowers the fluidity during molding; it thermally decomposes to generate hydrogen halide, corrodes the mold, and deteriorates or colors the resin itself. In addition, there is a problem of deteriorating the working environment. That is, a resin composition containing a halogen compound is unfavorable for the environment because it may generate harmful dioxins during combustion.
[0004]
For this reason, adding flame retardants other than organic halogen compounds has been studied.
[0005]
Examples of flame retardants other than organic halogen compounds include inorganic compound flame retardants such as aluminum hydroxide and magnesium hydroxide. However, these compounds have a remarkably low flame-retarding effect as compared with the organic halogen compounds. For this reason, in order to obtain a sufficient flame retarding effect, it is necessary to add a large amount, and there is a disadvantage that the original properties of the resin are impaired by the large amount addition.
[0006]
As a flame retardant resin composition free from organic halogen compounds that solves such problems, JP-A-4-298554 discloses that a phosphate ester and a polyorganosiloxane are added to a resin composition comprising an aromatic polycarbonate and an ABS resin. An excellent flame-retardant resin composition that has passed UL94SVA and CSA even with a blended molded article thinner than 2.8 mm has been proposed.
[0007]
[Problems to be solved by the invention]
In recent years, there is an increasing demand for cost reduction and weight reduction of various devices, and in response to such requests, housing materials, enclosure materials, and the like of OA devices tend to become thinner. In particular, the parts of the paper feed unit and paper discharge unit of the printer are required to have better sliding properties.
[0008]
Therefore, the development of a flame retardant resin composition that satisfies such requirements, has higher impact resistance and slidability, and is further superior in flame retardancy without using an organic halogen compound. It is desired.
[0009]
The present invention has been made in view of the above-described conventional circumstances, and an object thereof is to provide a flame retardant resin composition that is remarkably excellent in impact resistance and slidability and that does not use an organic halogen compound. .
[0010]
[Means for Solving the Problems]
The flame retardant resin composition of the present invention is
(A) 40 to 95% by weight of an aromatic polycarbonate resin, and (B) an aromatic vinyl monomer, a vinyl cyanide monomer, and other copolymerizable monomers used as necessary in the presence of a rubbery polymer. 5 to 60% by weight of a rubber-containing graft copolymer obtained by graft polymerization of the above monomer, (C) an aromatic vinyl monomer, a vinyl cyanide monomer, and a copolymer which can be used as necessary A basic resin composition comprising 50% by weight or less of a hard copolymer obtained by copolymerizing other monomers;
With respect to 100 parts by weight of the basic resin composition,
(D) 5 to 20 parts by weight of a phosphate ester flame retardant,
(E) Polyorganosiloxane graft copolymer 0 obtained by graft copolymerizing a polyorganosiloxane with a polyolefin-based thermoplastic resin selected from polyethylene, polypropylene, ethylene-methyl methacrylate copolymer, and ethylene-vinyl acetate copolymer 0.1 to 10 parts by weight is blended.
[0011]
According to the present invention, by blending a predetermined amount of a phosphate ester-based flame retardant and a polyorganosiloxane graft copolymer with a basic resin composition having a predetermined component composition, it is excellent without using an organic halogen compound. A flame retardant resin composition having a flame retarding effect and having high impact resistance and good slidability can be obtained.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the flame-retardant resin composition of the present invention will be described in detail.
[0013]
Examples of the aromatic polycarbonate resin (A) used in the present invention include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2- Bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) Bis (hydroxyaryl) alkane-based polycarbonates obtained from bis (hydroxyaryl) alkanes such as propane and bis (4-hydroxyphenyl) phenylmethane and carbonate esters (transesterification method) such as phosgene (phosgene method) or diaryl carbonate Examples thereof include resins. These may be used alone or in combination of two or more.
[0014]
Specific examples of the rubber-containing graft copolymer (B) used in the present invention include ABS resin, AES resin, AAS resin and the like.
[0015]
Examples of the rubber component in the rubber-containing graft copolymer (B) include polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, and ethylene-propylene-nonconjugated diene copolymer rubber (EPDM). Or 2 or more types can be used. In addition, as diolefin contained in EPDM, dicyclopentadiene, 1,4-hexadiene, 1,4-heptadiene, 1,5-cyclooctadiene, 6-methyl-1,5-heptadiene, 11-ethyl- Examples include 1,11-tridecadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, methyltetrahydroindene, limonene and the like.
[0016]
Examples of the aromatic vinyl monomer component used in the production of the rubber-containing graft copolymer (B) include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinyl xylene, monochloro. Styrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene and the like, preferably styrene, α-methylstyrene, and one or two of these The above can be used. Examples of the vinyl cyanide monomer component include acrylonitrile and methacrylonitrile, and one or more of these can be used.
[0017]
In the production of the rubber-containing graft copolymer (B) used in the present invention, in addition to the above-mentioned aromatic vinyl monomer component and vinyl cyanide monomer component, monomers copolymerizable therewith are used. It can be used as long as the object of the invention is not impaired. Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl (meth) acrylate (“(meth) acrylate” is “acrylate and / or methacrylate”) Α, β-unsaturated carboxylic acid esters such as ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; Α, β-unsaturated dicarboxylic acid anhydrides such as acid and itaconic anhydride; α, β-unsaturated compounds such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-o-chlorophenylmaleimide Examples include dicarboxylic acid imide compounds, and one or more of these monomers Can be used.
[0018]
There is no restriction | limiting in particular about the manufacturing method of a rubber containing graft copolymer (B), Generally well-known methods, such as block polymerization, solution polymerization, block suspension polymerization, suspension polymerization, and emulsion polymerization, are used. There are no particular restrictions on the compounding ratio of the rubbery polymer component, aromatic vinyl monomer component, vinyl cyanide monomer component and other copolymerizable monomer components used as necessary. Depending on the application, each component is appropriately blended. It is also possible to obtain a rubber-containing graft copolymer (B) by blending separately copolymerized resins.
[0019]
Generally, the blending ratio of each component of the rubber-containing graft copolymer (B) is as follows.
[ Rubber-containing graft copolymer (B) blend (wt%) ]
Rubber polymer component: 30-70
Aromatic vinyl monomer component: 18-56
Vinyl cyanide monomer component: 9 to 28
Other copolymerizable monomer components: 0 to 56
[0020]
The hard copolymer (C) used in the present invention is a copolymer comprising an aromatic vinyl monomer component, a vinyl cyanide monomer component, and other copolymerizable monomer components used as necessary. It is. Specific examples of these components include those described above in relation to the rubber-containing graft copolymer (B), and the composition ratio thereof is not particularly limited and is appropriately selected depending on the application. Examples of preferred hard copolymers include SAN resins, styrene-acrylonitrile-α-methylstyrene copolymers, styrene-acrylonitrile-N-phenylmaleimide copolymers, and the like. Moreover, there is no restriction | limiting in particular regarding the manufacturing method of this hard copolymer (C), Usually well-known methods, such as block polymerization, solution polymerization, block suspension polymerization, suspension polymerization, and emulsion polymerization, are used.
[0021]
Generally, the compounding ratio of each component of the hard copolymer (C) is as follows.
[ Hard copolymer (C) blend (wt%) ]
Aromatic vinyl monomer component: 60-80
Vinyl cyanide monomer component: 20-40
Other copolymerizable monomer components: 0-50
[0022]
A basic resin composition comprising an aromatic polycarbonate resin (A), a rubber-containing graft copolymer (B) and a hard copolymer (C) according to the present invention is known. The composition ratio of the basic resin composition is influenced by the rubber content in the rubber-containing graft copolymer (B), but the mechanical properties, thermal properties, and fluidity of the resulting resin composition, for example, In order to maintain strength characteristics, impact resistance, high rigidity, dimensional stability, heat resistance, fluidity, etc. within the desired ranges, the aromatic polycarbonate resin (A) component is 40 to 95% by weight of the base resin composition. The rubber-containing graft copolymer (B) component is used in an amount of 5 to 60% by weight, preferably 10 to 20% by weight of the base resin composition. The copolymer (C) component is used in an amount of 50% by weight or less, preferably 15% by weight or less of the basic resin composition.
[0023]
Examples of the phosphate ester flame retardant (D) used in the present invention include compounds represented by the following general formula (I).
[0024]
[Chemical formula 2]

[0025]
In the general formula ^(I), R a ~R carbon atoms hydrocarbon group ^c is preferably 2 to 16, particularly preferably from 6 to 10. Examples of hydrocarbon groups include alkyl groups, cycloalkyl groups, aralkyl groups, unsubstituted aryl groups, and substituted aryl groups. Substituted aryl groups include alkaryl groups, cycloalkylalkaryl groups, and aryl substituents. Examples include alkaryl groups and aryl-substituted aryl groups. Examples of alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, neopentyl, 3,5,5-trimethylhexyl, 3-methylhexyl, 2-ethylhexyl and 2, 5,5-trimethylhexyl is mentioned. Examples of cycloalkyl groups include cyclohexyl. Examples of aralkyl groups include benzyl and phenethyl. Examples of unsubstituted aryl groups include phenyl and naphthyl. Examples of alkaryl groups are o-, p- and m-tolyl, 2,6- and 2,4-dimethylphenyl, trimethylphenyl, o-, p- and m-isopropylphenyl, nonylphenyl, pt- Examples include butylphenyl, 2,4-diisopropylphenyl and triisopropylphenyl. An example of a cycloalkyl group is o-cyclohexylphenyl. Examples of aryl substituted alkaryl groups include p-benzylphenyl and p-phenethylphenyl. An example of an aryl-substituted aryl group is diphenyl.
[0026]
In the general formula (I), R ^a , R ^b and R ^c are preferably aryl groups or alkaryl groups, and in particular, phenyl, o-, p- and m-tolyl, 2,6-dimethylphenyl and 2,4-Diisopropylphenyl is preferred.
[0027]
Specific examples of the phosphate ester flame retardant (D) used in the present invention include the following.
[0028]
Trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) ) Phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate and bis (chloropropyl) monooctyl phosphate, substituents As alkoxy such as methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy such as Phenoxy, methyl (substituted) bisphenol A bisphosphate having a phenoxy, hydroquinone bisphosphate, resorcinol bisphosphate, trioxybenzene phosphate and the like. Preferably, triphenyl phosphate and various bisphosphates are used.
[0029]
The polyorganosiloxane graft copolymer (E) used in the present invention is a polyorganosiloxane represented by the following general formula (II) , from polyethylene, polypropylene, ethylene-methyl methacrylate copolymer, and ethylene-vinyl acetate copolymer. It is obtained by graft copolymerizing a selected polyolefin-based thermoplastic resin.
[0030]
[Chemical 3]

[0031]
In the above formula (II), as specific examples of R ^{1 to} R ⁸ , in the case of an aromatic hydrocarbon group, an aryl group such as phenyl, xylyl, and tolyl; a halogenated aryl group such as chlorophenyl; phenylethyl, benzyl In the case of an aliphatic hydrocarbon group, an alkyl group such as methyl, ethyl and propyl; an alkenyl group such as vinyl, propenyl and butenyl; a cyanoalkyl group such as cyanoethyl and cyanobutyl; a haloalkyl such as chlorobutyl and the like Group and the like, and in the case of an alicyclic hydrocarbon group, cyclohexyl and the like are mentioned. R ^{1 to} R ⁸ may all be the same or different from each other. R ^{1 to} R ⁸ are preferably selected from methyl, phenyl and vinyl.
[0032]
The polyorganosiloxane represented by the above formula (II) is used by adding a reactive functional group, for example, an epoxy group, amino group, carboxylic acid group, carboxylic acid ester group, mercapto group, hydroxyl group, etc. to a part thereof. May be. Moreover, you may use the vinyl group containing polyorganosiloxane which added the unsaturated group .
[0033]
Po polyorganosiloxane graft copolymer (E) is a said polyorganosiloxane 30-70 wt% and the previous SL 70-30 wt% polyolefin thermoplastic resin, in the presence or absence of an organic peroxide It can be manufactured by kneading.
[0034]
Specifically, as the polyorganosiloxane graft copolymer (E), a vinyl functional group-containing polyorganosiloxane in which a part of R ^{1 to} R ⁸ contains an unsaturated vinyl group in the formula (II) is 60% by weight. And polyorganosiloxane graft copolymer “SP-110” (trade name, manufactured by Dow Corning Asia Ltd.) obtained by graft copolymerization with 40% by weight of ethylene-vinyl acetate copolymer.
[0035]
In the present invention, an excellent flame retarding effect is obtained with an excellent synergistic effect by using the phosphate ester flame retardant (D) and the polyorganosiloxane graft copolymer (E) in combination, and the polyorganosiloxane graft copolymer By the combined body (E), characteristics such as good impact resistance and slidability are obtained, and heat resistance is also good. In order to obtain such a synergistic effect of each component without impairing the physical properties of the basic resin composition, in the present invention, with respect to 100 parts by weight of the basic resin composition,
Phosphate ester flame retardant (D): 5 to 20 parts by weight, preferably 9 to 15 parts by weight Polyorganosiloxane graft copolymer (E): 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight Mix parts.
[0036]
When the polyorganosiloxane graft copolymer (E) is less than 0.1 parts by weight, flame resistance of UL94 standard V-2 or higher cannot be obtained, and when it exceeds 5 parts by weight, the rigidity is lowered, and flame retardancy is also achieved. Deteriorate.
[0037]
In the present invention, a fluorinated hydrocarbon obtained by polymerizing tetrafluoroethylene as a main component, for example, polytetrafluoroethylene, may be further blended as an anti-drip agent. In this case, the blending amount of polytetrafluoroethylene is preferably 0.01 to 2 parts by weight, particularly 0.05 to 1.0 parts by weight, with respect to 100 parts by weight of the base resin composition.
[0038]
In addition to the above-mentioned components, the flame-retardant resin composition of the present invention, as long as the physical properties are not impaired, other additives commonly used at the time of molding (mixing) and molding of the resin composition, For example, pigments, dyes, fillers (carbon black, silica, titanium oxide, etc.), heat resistance agents, oxidation degradation inhibitors, weathering agents, lubricants, mold release agents, plasticizers, antistatic agents, and the like can be added.
[0039]
There is no restriction | limiting in particular in the method of manufacturing such a flame-retardant resin composition of this invention, It can manufacture using the method and apparatus currently performed normally. As a generally used method, there is a melt mixing method, and examples of the apparatus include an extruder, a Banbury mixer, a roller, and a kneader. This production may be either a batch type or a continuous type, and there is no particular limitation on the mixing order of the components, and it is sufficient that all the components are completely mixed.
[0040]
【Example】
EXAMPLES The present invention will be described more specifically with reference to the following examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
[0041]
Aromatic polycarbonate resins (A), rubber-containing graft copolymers (B), hard copolymers (C), phosphate ester flame retardants (D), and polyorganosiloxane grafts used in Examples and Comparative Examples The copolymer (E) is as follows:
(A) Aromatic polycarbonate resin:
Panlite L-1250 (manufactured by Teijin Chemicals Ltd.) (aromatic polycarbonate resin (B) rubber-containing graft copolymer obtained from 2,2-bis (4-hydroxyphenyl) propane and phosgene:
Graft copolymer B-1: ABS resin polybutadiene by emulsion polymerization 50% by weight
Styrene 35% by weight
Acrylonitrile 15% by weight
Graft copolymer B-2: AAS resin acrylate rubber by emulsion polymerization 50% by weight
Styrene 35% by weight
Acrylonitrile 15% by weight
(C) Rigid copolymer: 74% by weight of SAN resin styrene by suspension polymerization
Acrylonitrile 26% by weight
(D) Phosphate ester flame retardant:
Triphenyl phosphate (TPP)
Product name “CR733S” manufactured by Daihachi Chemical Co., Ltd. (aromatic phosphoric acid oligomer having the following structural formula (where n is an integer of 1 or more))
[0042]
[Formula 4]

(E) Polyorganosiloxane graft copolymer:
Product name “SP-110” manufactured by Dow Corning Asia Ltd.
Examples 1-8, Comparative Examples 1-5
Each component was mixed with a Henschel mixer at a blending ratio shown in Tables 2 and 3, and kneaded and pelletized with an extruder. The obtained pellets were injection molded at 260 ° C. to obtain a molded product. The obtained molded article was evaluated for various physical properties and flame retardancy by the following test methods, and the results are shown in Tables 2 and 3.
[0044]
(1) Izod impact strength (Kg · cm / cm): Measured according to ASTM D 256 with a thickness of 1/8 inch and notched.
(2) Flexural modulus (Kg / cm ² ): Measured according to ASTM D790.
(3) Thermal deformation temperature (° C.): Measured according to ASTM D 648-56.
(4) Coefficient of dynamic friction (-): Measured according to JIS K7218-A method.
Test condition partner material: Polyokine methylene Test load: 1.5kg
Test speed: 100mm / sec
(5) Flame retardancy: The test was carried out at a thickness of 1/10, 1/12, and 1/16 inch according to the test method of UL94 standard. Any of UL-94 V-0, V-1, V-2 and HB based on the test result of the sample material (number of samples for V evaluation: 5, number of samples for HB evaluation: 3) Rated to grade. The outline of the standard of each grade is as follows.
[0045]
[Table 1]

[0046]
[Table 2]

[0047]
[Table 3]

[0048]
As is apparent from Tables 2 and 3, the flame retardant resin composition of the present invention (Examples 1 to 8) exhibits good properties in terms of physical properties such as impact strength, flexural modulus, thermal deformation temperature, and slidability. , 1/10 ", 1/12", and 1/16 "all of the test pieces showed excellent flame retardancy.
[0049]
In contrast, the resin compositions (Comparative Examples 1 to 5) outside the scope of the present invention are inferior in flame retardancy and / or other physical properties. In particular, those in which the polyorganosiloxane graft copolymer of Comparative Examples 1 and 5 is not blended and Comparative Examples 2 and 4 in which the polyorganosiloxane graft copolymer is blended in a large amount have a low flexural modulus and flame resistance. The characteristic is bad. Further, in the case of blending polymethylphenyl silicone instead of the polyorganosiloxane graft copolymer of Comparative Example 3, sufficient flame retardancy was not obtained.
[0050]
【The invention's effect】
As described above in detail, the flame-retardant resin composition of the present invention is excellent in impact resistance, strength properties such as rigidity and flame retardancy, slidability, fluidity, thermal stability, etc., particularly impact resistance, Because it is extremely excellent in slidability and flame retardancy, it can fully meet the demands of OA equipment housing materials, enclosure materials, etc. in order to fully demonstrate its properties even in thin molded products, It is very useful industrially. In addition, since an organic halogen compound is not used as a flame retardant, it is very useful from the viewpoint of environmental problems.

Claims (2)

(A) 40 to 95% by weight of an aromatic polycarbonate resin, and (B) an aromatic vinyl monomer, a vinyl cyanide monomer, and other copolymerizable monomers used as necessary in the presence of a rubbery polymer. 5 to 60% by weight of a rubber-containing graft copolymer obtained by graft polymerization of the above monomer, (C) an aromatic vinyl monomer, a vinyl cyanide monomer, and a copolymer which can be used as necessary A basic resin composition comprising 50% by weight or less of a hard copolymer obtained by copolymerizing other monomers;
With respect to 100 parts by weight of the basic resin composition,
(D) 5 to 20 parts by weight of a phosphate ester flame retardant,
(E) Polyorganosiloxane graft copolymer 0 obtained by graft copolymerizing a polyorganosiloxane with a polyolefin-based thermoplastic resin selected from polyethylene, polypropylene, ethylene-methyl methacrylate copolymer, and ethylene-vinyl acetate copolymer 1 to 5 parts by weight of a flame retardant resin composition. The polyorganosiloxane graft copolymer according to claim 1, wherein the polyorganosiloxane graft copolymer has the following general formula: (II) R in the formula ¹ ~ R ⁸ A polyorganosiloxane graft copolymer obtained by graft copolymerizing 60% by weight of a vinyl functional group-containing polyorganosiloxane partially containing unsaturated vinyl groups and 40% by weight of an ethylene-vinyl acetate copolymer A flame retardant resin composition characterized by being: