JPH0543744B2 - - Google Patents
Info
- Publication number
- JPH0543744B2 JPH0543744B2 JP58100324A JP10032483A JPH0543744B2 JP H0543744 B2 JPH0543744 B2 JP H0543744B2 JP 58100324 A JP58100324 A JP 58100324A JP 10032483 A JP10032483 A JP 10032483A JP H0543744 B2 JPH0543744 B2 JP H0543744B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- parts
- styrene
- polyphenylene ether
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- -1 poly(2,6-dimethyl-1,4-phenylene) Polymers 0.000 claims description 20
- 229920001955 polyphenylene ether Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 10
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920001890 Novodur Polymers 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 5
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 229920005669 high impact polystyrene Polymers 0.000 claims 1
- 239000004797 high-impact polystyrene Substances 0.000 claims 1
- 229920001897 terpolymer Polymers 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、ポリフエニレンエーテル系樹脂と、
スチレン系樹脂のポリマー組成物に、ハロゲン化
アンモニウムを配合せしめた、極めて難燃性に優
れた熱可塑性樹脂組成物に関する。
ポリフエニレンエーテル系樹脂とスチレン系樹
脂のポリマー組成物は、機械的特性、熱的物性、
電気的特性等に優れ、尚かつ加工性が良く、家電
部品、配電部品、自動車部品、精密機械部品等に
広く用いられ、近年その需要の伸びは著しく、有
用な材料である。
一方、樹脂に対する産業界の要求性能のひとつ
としては、難燃化があげられる。米国のUL規格
等に見られる如く、樹脂の難燃化規則は厳しさを
増し、その対応が求められており、ポリフエニレ
ンエーテル系樹脂とスチレン系樹脂のポリマー組
成物も例外ではない。
この要求に答えるべく、該ポリマー組成物に、
芳香族リン酸エステルを配合させたもの（特公昭
53−418、特開昭53−73248）や有機ハロゲン化
物、若しくは有機ハロゲン化物と三酸化アンチモ
ンを併用し配合したもの（特開昭48−7945、特開
昭51−74038、特開昭52−128946）や、元素リン
を配合したもの（USP3663654）等の技術が公開
されているが、いずれも充分とは言えない。即ち
芳香族リン酸エステルを用いた場合の耐熱性低
下、有機ハロゲン化物、三酸化アンチモンを用い
た場合の耐衝撃性の低下や、三酸化アンチモンが
医薬用外劇物である故の作業性の悪さ、元素リン
を用いた場合の樹脂への赤着色化等、充分満足の
ゆく様な難燃剤は開発されておらず、ポリフエニ
レンエーテル系樹脂と、スチレン系樹脂のポリマ
ー組成物の優れた性能を損う事なく、しかも経済
的に難燃化する事は強く求められている。
本発明者等は、この要求に答えるべく、鋭意研
究を続けた結果、ハロゲン化アンモニウムが、ポ
リフエニレンエーテル系樹脂と、スチレン系樹脂
のポリマー組成物に極めて優れた難燃性を付与す
ることを見出し、本発明を完成するに到つた。
即ち本発明は、ポリフエニレンエーテル系樹脂
とスチレン系樹脂よりなるポリマー組成物100重
量部に対し、臭化アンモニウム0.05〜15重量部を
配合した、極めて難燃性に優れた熱可塑性樹脂組
成物を提供する。
更に本発明は、芳香族リン酸エステルを配合し
た場合に見られる様な、熱変形温度の低下や、有
機ハロゲン化物、若しくは有機ハロゲン化物と三
酸化アンチモンを併用配合した場合に見られる様
な、耐衝撃性の低下、熱安定性の低下という、樹
脂を難燃化する事により生ずる熱的、機械的物性
の低下を引き起こす事なく、しかも経済的に難燃
化を達成できる樹脂組成物を提供する。
本発明にいうポリフエニレンエーテル系樹脂と
は、一般式
（式中、R1、R2、R4、R5、R6は同一又は異なる
tert−ブチル基を除く炭素数１〜４のアルキル
基、アリール基、ハロゲン、水素等の一価の残基
であり、R5、R6は同時に水素ではない。）
を繰り返し単位とし、構成単位が〔〕又は
〔〕および〔〕からなる単独重合体あるいは
共重合体が使用できる。
PPEの単独重合体の代表例としては、ポリ
（２，６−ジメチル−１，４−フエニレン）エー
テル、ポリ（２−メチル−６−エチル−１，４−
フエニレン）エーテル、ポリ（２，６−ジエチル
−１，４−フエニレン）エーテル、ポリ（２−エ
チル−６−ｎ−プロピル−１，４−フエニレン）
エーテル、ポリ（２，６−ジ−ｎプロピル−１，
４−フエニレン）エーテル、ポリ（２−メチル−
６−ｎブチル−１，４−フエニレン）エーテル、
ポリ（２−エチル−６−イソプロピル−１，４−
フエニレン）エーテル、ポリ（２−メチル−６−
クロル−１，４−フエニレン）エーテル、ポリ
（２−メチル−６−ヒドロキシエチル−１，４−
フエニレン）エーテル、ポリ（２−メチル−６−
クロロエチル−１，４−フエニレン）エーテル等
のホモポリマーが挙げられる。
ポリフエニレンエーテル共重合体は、一般式
（ここにR3、R4、R5、R6は上記と同一の意味を
有する。）で表わされる２，３，６−トリメチル
フエノール等のアルキル置換フエノールと例え
ば、Ｏ−クレゾール等とを共重合して得られるポ
リフエニレンエーテル構造を主体としてなるポリ
フエニレンエーテル共重合体を包含する。
本発明に使用し得るスチレン系樹脂は、具体的
には、次式：
（式中、Ｒは水素、低級アルキルまたはハロゲン
を示し、Ｚはビニル、水素、塩素および低級アル
キルよりなる群から選択され、ｐは０〜５の整数
である）で表わされる化合物から誘導されるポリ
マー単位を少なくとも25重量％有するものであ
る。本明細書で使用する用語「スチレン系樹脂」
は、上記の式で定義され、例示すると、ホモポリ
マー、例えばポリスチレンおよびポリクロロスチ
レン、変性ポリスチレン、例えばゴム変性ポリス
チレンならびにスチレン含有コポリマー、例えば
スチレン−アクリロニトリルコポリマー
（SAN）、スチレン−ブタジエンコポリマー、ス
チレン−アクリロニトリル−ブタジエンコポリマ
ー（ABS）、ポリα−メチルスチレン、エチルビ
ニルベンゼンとジビニルベンゼンのコポリマーな
どを包含する。
本発明に好適なスチレン樹脂成分は、ゴム変性
耐衝撃性スチレン樹脂、例えば天然または合成ゴ
ムで変性されたポリスチレンである。変性用合成
ゴムは、例えばポリブタジエン、ポリイソプレ
ン、ジエンと他のコモノマー、例えばスチレン、
アクリロニトリル、アクリル酸エステルなどとよ
りなり、Ａ−Ｂ−ＡおよびＡ−Ｂ型（Ａはビニル
芳香族、例えばスチレン、Ｂはジエン、例えばブ
タジエン）のブロツクコポリマーを含むゴム状コ
ポリマーならびにエチレン−プロピレン−ジエン
タ−ポリマー（EPDM）ゴムなどである。ポリ
スチレンをブタジエンゴムで変性するのがもとつ
も好適である。
本発明では、ポリフエニレンエーテル系樹脂と
スチレン系樹脂の混合比は任意で良いが、好まし
くは、ポリフエニレンエーテル系樹脂90〜10重量
部に対し、スチレン系樹脂10〜90重量部が良く、
更に好ましくは、ポリフエニレンエーテル系樹脂
70〜30重量部に対し、スチレン系樹脂30〜70重量
部が良い。ポリフエニレンエーテル系樹脂が90重
量部以上では、該樹脂とスチレン系樹脂の混合組
成物の加工性が極めて低下し実用的でなく、また
スチレン系樹脂が90重量部以上では、熱変形温度
が充分満足のゆくものとならない。
又、本発明では、ポリフエニレンエーテル系樹
脂とスチレン系樹脂のポリマー組成物100重量部
に、ハロゲン化アンモニウム0.05〜15重量部を配
合する訳だが、0.05重量部以下では、樹脂に難燃
性を付与できず、また15重量部以上では、樹脂を
成型加工した時、成型品の外観を劣悪にしたり、
耐衝撃性を極めて低下させ好ましくない。ポリフ
エニレンエーテル系樹脂とスチレン系樹脂のポリ
マー組成物100重量部に更に好ましくは0.1〜10重
量部の添加である。
また本発明に用いる臭化アンモニウムは、樹脂
への分散性を向上させるために、通常用いられる
いかなる方法を持つて前処理或は後処理されても
よい。即ちシラン系等の表面処理剤を用いてもよ
い。更には通常、樹脂を安定化するために用い
る、酸化防止剤、紫外線吸収剤やその他の安定剤
を配合したり、樹脂を強化するためにガラス繊維
やその他の無機フイラーを用いる事は本発明を妨
げるものではない。
本発明の難燃化樹脂組成物の製造方法は、通常
樹脂を溶融、可塑化し、造粒、加工する如何なる
方法を用いても良い。例えば、ポリフエニレンエ
ーテル系樹脂、スチレン系樹脂、ハロゲン化アン
モニウムをドライブレンドし、押出機、加熱ロー
ル、バンバリーミキサー、ニーダー等を用い、樹
脂部を溶融せしめ、臭化アンモニウムを分散させ
る方法や、臭化アンモニウムを水に溶解させ、こ
の水溶液と樹脂を湿式ブレンドした後、上記と同
様の方法で、臭化アンモニウムを分散させる方法
や、ペント付押出機を用いて、ペント孔より臭化
アンモニウムを添加する方法等によつてもよい。
以下に本発明を一層明確にするために、実施例
を挙げて説明するが、本発明はこれにより範囲を
限定されるものではない。
実施例 １〜６
30℃におけるクロロホルム溶液（5wt／Vol.
％）の極限粘度が0.60dl／ｇのポリ（２，６−ジ
メチル−１，４−フエニレン）エーテルと、ポリ
ブタジエンを７重量％含むゴム変性ポリスチレン
と臭化アンモニウムを表−１に示す配合にて、ブ
レンダーで混合した後、真空ベント付二軸押出機
を用いて、表−１に示す温度にて溶融、押出を行
ないペレツトを得た。このペレツトを用いて表−
１に示す温度にて射出成形を行ない試験片を得
た。得られた試験片を用いて、Underwriters
Laboratory（UL）Bulletin No.94に従つて、1.6
mm厚試験片の火炎遅延性を評価した。また
ASTM規準に従つて物性を評価した。これらの
結果を表−１に示す。
比較例 １〜２
実施例１〜６と同様のポリ（２，６−ジメチル
−１，４−フエニレン）エーテルと、ゴム変性ポ
リスチレンを、表−１に示す組成で配合し、実施
例１〜６と同様の方法で、ブレンド・造粒・成形
し、評価した結果を表−１に比較例として示す。
表−１より明らかな様に、臭化アンモニウムの
添加により、ポリ（２，６−ジメチル−１，４−
フエニレン）エーテルとゴム変性ポリスチレンの
樹脂混合物は広範な混合比率の範囲において優れ
た難燃効果を付与され、尚かつ、加熱変形温度、
耐衝撃性の際立つた低下はない。
The present invention provides a polyphenylene ether resin;
This invention relates to a thermoplastic resin composition with extremely excellent flame retardancy, which is made by blending ammonium halide into a styrene-based resin polymer composition. The polymer composition of polyphenylene ether resin and styrene resin has mechanical properties, thermal properties,
It has excellent electrical properties and good workability, and is widely used in home appliance parts, power distribution parts, automobile parts, precision machine parts, etc., and its demand has increased significantly in recent years, making it a useful material. On the other hand, one of the performance requirements for resins in the industry is flame retardancy. As seen in the UL standards in the United States, flame retardant regulations for resins are becoming increasingly strict and compliance is required, and polymer compositions of polyphenylene ether resins and styrene resins are no exception. In order to meet this demand, the polymer composition includes
Formulated with aromatic phosphate ester (Tokukosho
53-418, JP-A-53-73248), organic halides, or combinations of organic halides and antimony trioxide (JP-A-48-7945, JP-A-51-74038, JP-A-52- 128946) and one containing elemental phosphorus (USP 3663654), but none of them can be said to be sufficient. In other words, there is a decrease in heat resistance when aromatic phosphate esters are used, a decrease in impact resistance when organic halides and antimony trioxide are used, and workability is reduced because antimony trioxide is a non-medicinal deleterious substance. No flame retardant has been developed that is fully satisfactory, such as red coloring of the resin when elemental phosphorus is used. There is a strong need to make flame retardant economically without compromising performance. In order to meet this demand, the present inventors continued intensive research and found that ammonium halides impart extremely excellent flame retardancy to polymer compositions of polyphenylene ether resins and styrene resins. They discovered this and completed the present invention. That is, the present invention provides a thermoplastic resin composition with extremely excellent flame retardancy, which contains 0.05 to 15 parts by weight of ammonium bromide to 100 parts by weight of a polymer composition consisting of a polyphenylene ether resin and a styrene resin. I will provide a. Furthermore, the present invention provides a reduction in heat distortion temperature, as seen when an aromatic phosphate ester is blended, and a reduction in heat distortion temperature, as seen when an organic halide or an organic halide and antimony trioxide are blended together. To provide a resin composition that can achieve flame retardancy economically without causing a decrease in thermal and mechanical properties caused by making the resin flame retardant, such as a decrease in impact resistance or thermal stability. do. The polyphenylene ether resin referred to in the present invention has the general formula (In the formula, R 1 , R 2 , R 4 , R 5 , R 6 are the same or different
It is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms excluding a tert-butyl group, an aryl group, a halogen, or hydrogen, and R 5 and R 6 are not hydrogen at the same time. ) can be used as a repeating unit, and a homopolymer or copolymer consisting of [ ] or [ ] and [ ] as constituent units can be used. Representative examples of PPE homopolymers include poly(2,6-dimethyl-1,4-phenylene) ether and poly(2-methyl-6-ethyl-1,4-
phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene)
ether, poly(2,6-di-n-propyl-1,
4-phenylene)ether, poly(2-methyl-
6-n-butyl-1,4-phenylene) ether,
Poly(2-ethyl-6-isopropyl-1,4-
phenylene)ether, poly(2-methyl-6-
Chlor-1,4-phenylene)ether, poly(2-methyl-6-hydroxyethyl-1,4-
phenylene)ether, poly(2-methyl-6-
Examples include homopolymers such as chloroethyl-1,4-phenylene) ether. Polyphenylene ether copolymer has the general formula (Here, R 3 , R 4 , R 5 , and R 6 have the same meanings as above.) A combination of an alkyl-substituted phenol such as 2,3,6-trimethylphenol and, for example, O-cresol, etc. It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure obtained by polymerization. Specifically, the styrenic resin that can be used in the present invention has the following formula: (wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, chlorine and lower alkyl, and p is an integer from 0 to 5) It has at least 25% by weight of polymer units. The term "styrenic resin" used herein
is defined in the above formula and includes, by way of example, homopolymers such as polystyrene and polychlorostyrene, modified polystyrenes such as rubber-modified polystyrene and styrene-containing copolymers such as styrene-acrylonitrile copolymers (SAN), styrene-butadiene copolymers, styrene- These include acrylonitrile-butadiene copolymer (ABS), poly-alpha-methylstyrene, and copolymers of ethylvinylbenzene and divinylbenzene. Styrenic resin components suitable for the present invention are rubber-modified impact styrenic resins, such as polystyrene modified with natural or synthetic rubber. Synthetic rubbers for modification include, for example, polybutadiene, polyisoprene, dienes and other comonomers such as styrene,
rubbery copolymers of the A-B-A and A-B types (where A is a vinyl aromatic, e.g. styrene and B is a diene, e.g. butadiene), and ethylene-propylene- Dienterpolymer (EPDM) rubber, etc. It is originally preferred to modify polystyrene with butadiene rubber. In the present invention, the mixing ratio of the polyphenylene ether resin and the styrene resin may be arbitrary, but it is preferably 10 to 90 parts by weight of the styrene resin to 90 to 10 parts by weight of the polyphenylene ether resin. ,
More preferably, polyphenylene ether resin
70 to 30 parts by weight of the styrene resin is preferably 30 to 70 parts by weight. If the polyphenylene ether resin is 90 parts by weight or more, the processability of the mixed composition of the resin and styrene resin will be extremely reduced, making it impractical, and if the styrene resin is 90 parts by weight or more, the heat distortion temperature will increase. It's not completely satisfying. In addition, in the present invention, 0.05 to 15 parts by weight of ammonium halide is blended into 100 parts by weight of the polymer composition of polyphenylene ether resin and styrene resin, but if it is less than 0.05 parts by weight, the resin will have flame retardant properties. If the amount exceeds 15 parts by weight, the appearance of the molded product may deteriorate when the resin is molded.
This is undesirable as it greatly reduces impact resistance. It is more preferably added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the polymer composition of polyphenylene ether resin and styrene resin. Further, the ammonium bromide used in the present invention may be pre-treated or post-treated by any commonly used method in order to improve its dispersibility in the resin. That is, a surface treatment agent such as a silane type may be used. Furthermore, the present invention does not include the addition of antioxidants, ultraviolet absorbers, and other stabilizers that are normally used to stabilize resins, and the use of glass fibers and other inorganic fillers to strengthen resins. It's not a hindrance. The method for producing the flame-retardant resin composition of the present invention may be any method in which a resin is normally melted, plasticized, granulated, and processed. For example, a method of dry blending polyphenylene ether resin, styrene resin, and ammonium halide, melting the resin part using an extruder, heating roll, Banbury mixer, kneader, etc., and dispersing ammonium bromide; After dissolving ammonium bromide in water and wet blending this aqueous solution with the resin, ammonium bromide can be dispersed using the same method as above, or ammonium bromide can be dispersed through the pent hole using an extruder with a pent. It may also depend on the method of addition. EXAMPLES In order to further clarify the present invention, the present invention will be described below with reference to Examples, but the scope of the present invention is not limited thereby. Examples 1 to 6 Chloroform solution (5wt/Vol.
%) with an intrinsic viscosity of 0.60 dl/g, rubber-modified polystyrene containing 7% by weight of polybutadiene, and ammonium bromide in the composition shown in Table 1. After mixing in a blender, melting and extrusion were performed using a vacuum vented twin-screw extruder at the temperatures shown in Table 1 to obtain pellets. Using this pellet,
Injection molding was performed at the temperature shown in 1 to obtain a test piece. Using the obtained test piece, Underwriters
According to Laboratory (UL) Bulletin No.94, 1.6
The flame retardation properties of mm-thick specimens were evaluated. Also
Physical properties were evaluated according to ASTM standards. These results are shown in Table-1. Comparative Examples 1-2 Poly(2,6-dimethyl-1,4-phenylene) ether similar to Examples 1-6 and rubber-modified polystyrene were blended in the composition shown in Table 1, and Examples 1-6 were prepared. The results of blending, granulation, and molding in the same manner as above and evaluation are shown in Table 1 as a comparative example. As is clear from Table 1, by adding ammonium bromide, poly(2,6-dimethyl-1,4-
A resin mixture of (phenylene) ether and rubber-modified polystyrene has an excellent flame retardant effect in a wide range of mixing ratios, and has a low heating distortion temperature,
There is no noticeable decrease in impact resistance.
【表】
実施例 ７〜８
実施例３、４の組成においてポリ（２，６−ジ
メチル−１，４−フエニレン）エーテルを極限粘
度〔η〕（クロロホルム、30℃）が0.65である２，
６−ジメチルフエノール（90モル％）と２，３，
６−トリメチルフエノール（10モル％）との共重
合体に置きかえる以外は全く同様の組成及び条件
で評価を行なつた。結果を表−２に示す。[Table] Examples 7 to 8 In the compositions of Examples 3 and 4, poly(2,6-dimethyl-1,4-phenylene) ether with an intrinsic viscosity [η] (chloroform, 30°C) of 0.65,
6-dimethylphenol (90 mol%) and 2,3,
Evaluation was carried out under exactly the same composition and conditions except that the copolymer with 6-trimethylphenol (10 mol %) was used. The results are shown in Table-2.
【表】【table】
Claims (1)
樹脂よりなるポリマー組成物100重量部に対し、
臭化アンモニウム0.05〜15重量部を配合せしめた
難燃化熱可塑性樹脂組成物。 ２ ポリフエニレンエーテル系樹脂が、ポリ
（2.6−ジメチル−1.4−フエニレン）エーテルで
ある特許請求の範囲第１項記載の組成物。 ３ ポリフエニレンエーテル系樹脂が、2.6−ジ
メチルフエノールと、2.3.6−トリメチルフエノ
ールとの共重合体である特許請求の範囲第１項記
載の組成物。 ４ スチレン系樹脂が、ゴム変性高耐衝撃性ポリ
スチレンである特許請求の範囲第１項記載の組成
物。 ５ スチレン系樹脂が、スチレン、アクリロニト
リル、ブタジエンの三元共重合体である特許請求
の範囲第１項記載の組成物。[Claims] 1. For 100 parts by weight of a polymer composition consisting of a polyphenylene ether resin and a styrene resin,
A flame-retardant thermoplastic resin composition containing 0.05 to 15 parts by weight of ammonium bromide. 2. The composition according to claim 1, wherein the polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene) ether. 3. The composition according to claim 1, wherein the polyphenylene ether resin is a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. 4. The composition according to claim 1, wherein the styrenic resin is rubber-modified high-impact polystyrene. 5. The composition according to claim 1, wherein the styrenic resin is a terpolymer of styrene, acrylonitrile, and butadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10032483A JPS59226046A (en) | 1983-06-07 | 1983-06-07 | Flame-retardant thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10032483A JPS59226046A (en) | 1983-06-07 | 1983-06-07 | Flame-retardant thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59226046A JPS59226046A (en) | 1984-12-19 |
| JPH0543744B2 true JPH0543744B2 (en) | 1993-07-02 |
Family
ID=14270991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10032483A Granted JPS59226046A (en) | 1983-06-07 | 1983-06-07 | Flame-retardant thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59226046A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS517494A (en) * | 1974-07-06 | 1976-01-21 | Tohoku Electric Power Co | DENSENCHAKUSETSUKEISOKUSOCHI |
| JPS5228461A (en) * | 1975-08-28 | 1977-03-03 | Kubota Ltd | Dry desulfurization apparatus |
| JPS57195147A (en) * | 1981-05-26 | 1982-11-30 | Mitsubishi Petrochem Co Ltd | Polyphenylene ether resin composition |
-
1983
- 1983-06-07 JP JP10032483A patent/JPS59226046A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS517494A (en) * | 1974-07-06 | 1976-01-21 | Tohoku Electric Power Co | DENSENCHAKUSETSUKEISOKUSOCHI |
| JPS5228461A (en) * | 1975-08-28 | 1977-03-03 | Kubota Ltd | Dry desulfurization apparatus |
| JPS57195147A (en) * | 1981-05-26 | 1982-11-30 | Mitsubishi Petrochem Co Ltd | Polyphenylene ether resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59226046A (en) | 1984-12-19 |
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