JPS59202240A - Flame-retardant thermoplastic resin composition - Google Patents
Flame-retardant thermoplastic resin compositionInfo
- Publication number
- JPS59202240A JPS59202240A JP7809283A JP7809283A JPS59202240A JP S59202240 A JPS59202240 A JP S59202240A JP 7809283 A JP7809283 A JP 7809283A JP 7809283 A JP7809283 A JP 7809283A JP S59202240 A JPS59202240 A JP S59202240A
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- polyphosphoric acid
- flame
- resin
- ester
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
本発明は直鎮状及び杖わかれ状構造を持ったポリ燐酸エ
ステルのｎ量体（ｎ−１〜１５）の混合された、酸価が
１５以下の特殊なポリ燐酸エスチルを難燃剤として含有
する難燃性熱可塑性樹脂組成物に関し、特に高度の難燃
性と、高温下において、低揮発性、耐熱性、耐ブリード
性、帯電性等との性質を兼ね備え、しかもその製造法が
経済的に有利な難燃性熱可塑性樹脂組成物を提供するこ
とを目的とし、宗匠用品から工業用品に至る捷で、例え
ば機械機構部品、電気部品、電子部品、自動車部品、合
成繊維なとに多く使用されるものでるる。Detailed Description of the Invention The present invention is a special polyphosphoric acid having an acid value of 15 or less, which is a mixture of n-mers (n-1 to 15) of polyphosphoric acid esters having straight and branched structures. Concerning flame-retardant thermoplastic resin compositions containing ester as a flame retardant, they have particularly high flame retardancy, low volatility under high temperatures, heat resistance, bleed resistance, electrostatic properties, etc. The purpose is to provide a flame-retardant thermoplastic resin composition whose manufacturing method is economically advantageous, and it can be used in everything from craft supplies to industrial supplies, such as mechanical parts, electrical parts, electronic parts, automobile parts, synthetic parts, etc. It is often used as a fiber.
従来難燃剤として使用されている有機燐化合物、例えば
トリフェニルホスフェート、クレジルジフェニルホスフ
ェート、トリクレジルホスフェート、インプロビルフェ
ニルジフェニルホスフエート等はあるが、然ＯｉＴ塑性
樹脂の耐熱性及び物性の低下、品温条件下における有機
燐化合物の揮発、しみ出し等の欠点があった。Although there are organic phosphorus compounds conventionally used as flame retardants, such as triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, and improbylphenyl diphenyl phosphate, they do not reduce the heat resistance and physical properties of natural OiT plastic resins, There were drawbacks such as volatilization and seepage of organic phosphorus compounds under temperature conditions.
」二記の欠点を解決する方法としてすでに分子量の人な
る有機燐化合物が熱可塑性樹脂の難燃剤として注１」さ
れている。As a way to solve the above two drawbacks, organic phosphorus compounds with a certain molecular weight have already been used as flame retardants for thermoplastic resins.
これに関しては、例えば特公昭５ｌ−ｔ９８５８号、特
公昭５１−３９２７１号、特開昭４９−２８５０号、特
開昭５”５−１１８９５７号、特開１召５７−２０７６
’４１り、特開昭５７−２０７６４２号等の発明がある
。Regarding this, for example, Japanese Patent Publication No. 51-t9858, Japanese Patent Publication No. 51-39271, Japanese Patent Application Publication No. 49-2850, Japanese Patent Publication No. 5"5-118957, Japanese Patent Publication No. 197-2076
There are inventions such as '41 and JP-A-57-207642.
これらの発明に代表される化合物は直鎮状のポリ燐酸エ
ステルでその構造式の代表的なものとして、
（Ｒ”Ｏ）２Ｆ ＯＲ”ＯＰ （ＯＲす２・・・・・・
・・・・・・・・・（１）Ｉ１１！
ｘｘ （特公昭５１−１９８５８号より９（式
中、Ｒ１、Ｒ２は同−又は異なるＩＩＩＩＩｌの芳香族
基、幻は２価の芳香族基、Ｘは酸素又は硫黄を示す、）
ＩＩ ＩＩ ＩＩＸ７
ｘ ｘ
（特公昭５１−３９２７１す°より）
（式中Ｒ１、Ｒ２は一価の芳香族基又は脂肪族基、Ｒ３
は二価の芳香族基、Ｘは酸素又は硫黄、ｎは正数）
を挙げることができる。The compounds represented by these inventions are linear polyphosphoric esters, and their typical structural formula is (R"O)2F OR"OP (ORS2...
・・・・・・・・・(1) I11! xx (From Japanese Patent Publication No. 51-19858, 9 (wherein, R1 and R2 are the same or different III aromatic groups, phantom is a divalent aromatic group, and X is oxygen or sulfur) II II IIX7
x x (From Japanese Patent Publication No. 51-39271) (In the formula, R1 and R2 are monovalent aromatic groups or aliphatic groups,
is a divalent aromatic group, X is oxygen or sulfur, and n is a positive number).
（１）の化合物はアリレンジオールとジアリールホスフ
ォ（チオ）タロリゾートを無溶謀或いは有機溶媒中で反
応させることによシ比較的容易に月つ高収率で君Ｊられ
る。The compound (1) can be produced relatively easily and in high yields by reacting arylene diol and diarylphospho(thio)taloresol without solvent or in an organic solvent.
捷た（２）の化合物は有機溶媒中或いは無溶媒で所定モ
ル数のアリレンジオールとアルキル又はアリールボスボ
リルジクロライドとを混合してエステル化を行ない、反
応終了後、ジアルキル又はジアリールホスホリルクロラ
イド或いはアルコール又はフェノールを加えて生成物の
両端をエステル化することによって比較的容易に且つ高
収率で得られるのである。The separated compound (2) is esterified by mixing a predetermined number of moles of arylene diol and alkyl or arylbosboryl dichloride in an organic solvent or without a solvent, and after the reaction is completed, dialkyl or diarylphosphoryl chloride or alcohol Alternatively, it can be obtained relatively easily and in high yield by adding phenol to esterify both ends of the product.
上記（１）及び（２）の化合物の製法の特徴は次の３点
である。The method for producing the compounds (1) and (2) above is characterized by the following three points.
（１）難燃性元素の燐源としてジアリールホスホロ（チ
オ）タロリゾート、アルキル又はアリールボスボリルジ
クロライド、ジアルキル又はジアリールホスホリルクロ
ライドを使用している。(1) Diarylphosphoro(thio)taloresort, alkyl or arylbosboryl dichloride, dialkyl or diarylphosphoryl chloride is used as the source of phosphorus, a flame retardant element.
（ＩＩ）反応して得られた生成物が直鎮状の化合物であ
る。(II) The product obtained by the reaction is a straight compound.
（Ｉｌｌ）末端が完全にエステル化されている。(Ill) The terminal is completely esterified.
上記ｆ１）及び（２）化合物は知、燃性元素の燐源とし
てジアリールホスホロ（チオ）クロリデート、アルキル
又はアリールホスホリルクロライド、ジアルキル又はジ
アリールホスホリルクロライド等を使用しているが、そ
の製造法、収率の点からして高価であり、経済的に不利
である。The above compounds f1) and (2) are known to use diarylphosphoro(thio)chloridate, alkyl or arylphosphoryl chloride, dialkyl or diarylphosphoryl chloride, etc. as a flammable element phosphorus source, but their production methods and yields are It is expensive in terms of efficiency and is economically disadvantageous.
一方、経済的に准″利な難燃性元系源としてオキシ塩化
丈４がある。このオキシ塩化燐と・・イドロキノンの如
き２価フェノール類とを反応させると得られたポリ燐酸
エステルは３次元構造となるため樹脂化して不溶不融の
ものとなり、実用に供し得ないのである。On the other hand, oxychloride 4 is an economically advantageous source of flame retardancy. Polyphosphoric acid ester obtained by reacting this phosphorus oxychloride with a dihydric phenol such as hydroquinone is 3 Because it has a dimensional structure, it turns into a resin and becomes insoluble and infusible, making it impossible to put it to practical use.
不発１タ］者等は然ＦＪＪ塑性樹脂に１叔加される難燃
剤について、熱硬化性樹脂の難燃剤として既に特公−昭
５４−３２８１８号公報に記載のあるオキシ塩化燐とＨ
ＯＡｒｌｏＨで表される二価フェノール類及びＡｒ２０
Ｈで表わされる１価フェノール類との反応によって得ら
れるポリ燐酸エステルのうち、該ポリ煽、！酸エステル
のｎ量体のｎ（ｎは１以上の整数で、分子中のｌ子の個
数を表わす、）が１〜１５の整数の混合物であり、ｎ＝
１の成分を４０重賦形以下含有し、かつ酸価が１５以下
のポリ鳴・酸エステルが熱可塑性樹脂に対して有効な難
燃剤であることを見出し、不発す」を完成するに至った
ものである。Regarding the flame retardants added to the FJJ plastic resin, those who have misexploded it are aware that phosphorus oxychloride and H
Dihydric phenols represented by OArloH and Ar20
Of the polyphosphoric acid esters obtained by reaction with monohydric phenols represented by H, the polyphosphoric acid,! n of the acid ester n-mer (n is an integer of 1 or more and represents the number of l molecules in the molecule) is a mixture of integers from 1 to 15, and n =
We discovered that a polyphonic acid ester containing 40 or less of component 1 and having an acid value of 15 or less is an effective flame retardant for thermoplastic resins, and completed the process of "non-exploding". It is something.
不発り」の熱可塑性樹脂組成物は上記ボＩＪ ４＝−酸
エステルを主成分として５〜３０重量％含有してなるも
のである。The thermoplastic resin composition containing 5 to 30% by weight of the above-mentioned BoIJ4=-acid ester as a main component.
ここにＡｒｌ、Ａｒ２は夫々間−又は相異なる芳香族基
である。Here, Arl and Ar2 are each an aromatic group or different aromatic groups.
更にまた先願の特公昭５４−３２８１８号発明は上を己
のようにしてイ仔られたポリ燐酸エステルのｎｌｌＬ体
が有するｎ＋２個の全末端が−Ａｒ１０Ｈ及び／又は−
Ａｒ２であることを必須要件としている。Furthermore, the earlier invention of Japanese Patent Publication No. 54-32818 discloses that all n+2 terminals of the nlllL body of a polyphosphoric acid ester prepared as above are -Ar10H and/or -
It is an essential requirement that it be Ar2.
即ち、末端が−Ａｒ工ＯＨの場合は熱硬化性樹脂の反応
型難燃剤として使用されるが、本発明では２価フェノー
ルの残基−Ａｒ□ＯＨは不要であり、むしろ同残基は熱
可塑性樹脂の着色の原因となり好ましくない、又末端が
−Ａｒ２の場合添加型難燃剤として使用されるが、本発
明は次に説明ごとを特徴としている。That is, when the terminal is -Ar□OH, it is used as a reactive flame retardant for thermosetting resins, but in the present invention, the residue of dihydric phenol -Ar□OH is not necessary; rather, the residue is used as a reactive flame retardant for thermosetting resins. This is undesirable because it causes coloration of the plastic resin, and when the terminal is -Ar2, it is used as an additive flame retardant, but the present invention is characterized by the following description.
不発り」のｎ ＝ １の成分が４０重量％を超過すると
耐熱性、高温下での揮発性が悪くなり、本発明の目的を
達成することができない。If the content of n = 1 component of "unexploded" exceeds 40% by weight, heat resistance and volatility at high temperatures will deteriorate, making it impossible to achieve the object of the present invention.
捷た本発明に使用のポリ燐酸エステルの酸価が１５を超
過すると両温における成形時、樹脂か劣化するし、酸価
が１未満の場合は帯電防止性が低下する。If the acid value of the shredded polyphosphoric acid ester used in the present invention exceeds 15, the resin will deteriorate during molding at both temperatures, and if the acid value is less than 1, the antistatic properties will decrease.
従って特に帯電防止性を期待しない場合はポリ燐酸エス
テルの酸価は１未満でも良く、樹脂の難燃性付与には差
支えない。Therefore, if antistatic properties are not particularly expected, the acid value of the polyphosphoric acid ester may be less than 1, which does not interfere with imparting flame retardancy to the resin.
本発明における２価のフェノール類としてはハイ ドロ
キノン、レゾルシノール、ビスフェノールＡ１ ビスフ
ェノールＦ１ ビスフェノールスルホン、これらの塩素
化物又はこれらの臭素化物等であり、それらの１種以上
が使用される。The divalent phenols used in the present invention include hydroquinone, resorcinol, bisphenol A1, bisphenol F1, bisphenol sulfone, chlorinated products thereof, or brominated products thereof, and one or more of these may be used.
また１価のフェノール類としてはフェノール、クレゾー
ル、キシレノール、イソプロピルフェノール、ブチルフ
ェノール、これらの塩素化物又はこれらの臭素化物等で
あり、それらの１種以上が使用される。Monovalent phenols include phenol, cresol, xylenol, isopropylphenol, butylphenol, chlorinated products thereof, or brominated products thereof, and one or more of these may be used.
不発り］の熱可塑性樹脂としてはポリフェニレンエーテ
ル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポ
リスチレン系樹脂、ポリカーボネート系樹脂、ポリオレ
フィン系樹脂等である。Examples of the thermoplastic resins for non-explosion include polyphenylene ether resins, polyester resins, polyamide resins, polystyrene resins, polycarbonate resins, and polyolefin resins.
ポリフェニレンエーテル樹脂とは、式
ルキル基、捷たはハロアルコキシ基であり、各々の炭素
数は１〜４個である。）で示されるフェノール類１′↓
を酸化カンプリングして得られる重合体である。特に好
ましいのはポリ（λ６−シメチルー１．４−フェニレン
）エーテルテアル。The polyphenylene ether resin is alkyl group, alkyl group, or haloalkoxy group, each having 1 to 4 carbon atoms. ) Phenols 1'↓
It is a polymer obtained by oxidative camping of Particularly preferred is poly(λ6-dimethyl-1,4-phenylene)ethertheal.
ポリフェニレンエーテル系樹脂とは上記ポリフェニレン
エーテル樹脂と他の樹脂、゛例えばポリスチレン、スチ
レン共重合体、ポリカーボネート、ポリスルホン、ナイ
ロン、ポリオレフィン又はゴム質重合体等との配合物、
又はポリフェニレンエーテル樹脂の存在下で他のモノマ
ー、例えばスチレン、エチレン、フロピレン、ブタジェ
ン等を重合させて得られるグラフト共重合体、またはポ
リスチレン、スチレン共重合体、ポリカーボネート、ナ
イロン、ポリオレフィンおよびゴム質重合体等の存在下
て上記の式で示される７エ／−ル類を酸化カンプリング
して得られた共重合体等である。Polyphenylene ether resin is a mixture of the above polyphenylene ether resin and other resins, such as polystyrene, styrene copolymer, polycarbonate, polysulfone, nylon, polyolefin, or rubbery polymer.
or graft copolymers obtained by polymerizing other monomers such as styrene, ethylene, flopylene, butadiene, etc. in the presence of polyphenylene ether resins, or polystyrene, styrene copolymers, polycarbonates, nylons, polyolefins, and rubbery polymers. These are copolymers obtained by oxidative camping of the 7-er/-ols represented by the above formula in the presence of the following.
上記の配合物、グラフト共重合体又は共重合体等に於け
るポリフェニレンエーテル樹脂と他の樹脂との組合せの
重量比は任意に行なうことが出来る。The weight ratio of the combination of the polyphenylene ether resin and other resins in the above-mentioned blends, graft copolymers, copolymers, etc. can be adjusted arbitrarily.
−またポリエステル系４１脂とはボ、す７エチレンテ・
浴
し７クレートとその共帆体及びポリブチレン７人
クレートである。ポリエチレンテレフクレートの共重合
体とはテレ７クール酸やエチレングリコールのほかにイ
ソ７クール酸、１゜２−プロピレンクリコール、１．３
−プチレンクｌ） ：Ｉ −／Ｌ／ ’４を２０〜３０
％共重合したポリエチレングリコ−／Ｌ／ ヲ王体とし
たポリエステルである。- Also, what is polyester-based 41 fat?
These are a bathing 7-person crate, its co-hull, and a polybutylene 7-person crate. What is the copolymer of polyethylene terephcrate?In addition to tele7curic acid and ethylene glycol, it also contains iso7curic acid, 1゜2-propylene glycol, and 1.3゜2-propylene glycol.
- Petite L): I-/L/'4 20-30
% copolymerized polyethylene glyco-/L/O-based polyester.
ポリアミド樹カ旨とは、ナイロン−６、ナイロン−６，
６である０丈にポリスチレン系樹カ旨とは一般用（Ｇ、
Ｐ。）ポリスチレンと耐衝撃性（Ｈニーｈｉｇｈ ｉｍ
ｐａｃｔ）ポリスチレンとである。Ｈエボリスチレンは
（Ｇ、Ｅ）ポリスチレンに合成ゴムＳＤＲ。The polyamide resin includes nylon-6, nylon-6,
6, which is 0 length, is polystyrene-based wood for general use (G,
P. ) Polystyrene and impact resistance (H knee high im
pact) polystyrene. H Evolistyrene is (G, E) polystyrene and synthetic rubber SDR.
ＢＲ等を５〜２０％配合したものでＧ。只ポリスチレン
のもろさを改良したものである。G contains 5 to 20% of BR etc. It is simply an improved brittle version of polystyrene.
次に本発明に使用されるポリ燐酸エステルの構造式につ
いては、ｎ ＝ ４の場合次式の２化合物が与えられる
・ 。＝ ４、＋ｍ 鋲の場合、ｏ ｏ
ｏ 。Next, regarding the structural formula of the polyphosphoric acid ester used in the present invention, when n = 4, two compounds of the following formula are given. = 4, +m For rivets, o o
o.
ＩＩ ＩＩ ＩＩ １１Ａ
ｒ２Ａｒ２ 、Ａｒ２Ａｒ２
ｎ ＝＝ ４、杖わかれ構造の場合
ｏｏｏ ｏ 。II II II 11A
r2Ar2, Ar2Ar2 n == 4, ooo o in case of cane-branched structure.
ＩＩ ＩＩ ＩＩ ＩＩ
ＩＩｒ２Ａｒ２
ｆ４］
（４つ即ち、オギシ塩化燐を使用した場合、ｎ ＝ ４
のポリ％酸エステルは直鎖状と枝わかれ状との構造式を
持った混合物である。II II II II
IIr2Ar2 f4]
(4, i.e., when using Ogishi phosphorus chloride, n = 4
Poly% acid ester is a mixture with linear and branched structural formulas.
同様にｎ ＝ ５以上のポリ燐酸エステルについても直
鎖状と枝わかれ状との横−造式を持った混合物を与える
のである。Similarly, for polyphosphoric acid esters with n=5 or more, a mixture having a horizontal structure of a linear structure and a branched structure is obtained.
本発明の特徴の一つば不発１月に使用のポリ燐酸エステ
ルの末端の一部が燐酸基
１
（） ＰＯＨ）になっていることである。One of the features of the present invention is that a portion of the terminal end of the polyphosphoric acid ester used in the unexploded product is a phosphoric acid group (1 () POH).
従来から燐酸基ｔ／′ｉ樹脂の劣化の原因と名えられて
いたか不発す」者等の研究の結果、酸価が１５以下好丑
しくば１〜７て？燐酸基を存在、せしめることによって
樹脂を劣化せしめないのみならず、むしろわ１脂に帯電
防止性を与える効果があることが゛トリ明したのである
。言うまてもなく樹脂の帯電防止性は特に電気機器のよ
うに高い精度をν末される機器の材料として重要な性質
である。As a result of research by those who have traditionally believed that phosphoric acid groups are the cause of deterioration of t/'i resins, acid values of 15 or less are preferable, or 1 to 7. It has been found that the presence of phosphoric acid groups not only does not cause the resin to deteriorate, but also has the effect of imparting antistatic properties to wax resin. Needless to say, the antistatic property of resin is an important property, especially as a material for equipment that requires high precision, such as electrical equipment.
次に不発［）］に便１」されるポリ燐酸エステルは後記
のボＩＪ ＩＪン酸エステルの製造法、その１〜その６
ＩＣ／Ｆすように例えばオキシ塩化取燐１モルに対し
て２価フェノール類（ＨＯＡｒ、ＯＨ，）を０．４８〜
０゜８７５モル反応せしめ、ついで１．２５〜２゜１０
モルの１価フェノール類（Ａｒ２０Ｈ）を灰層せしめて
得られるが、最終ｌ」的物のポリ燐酸エステルの酸価は
１価フェノール類の仕込み量によって−「”ｊ整される
。Next, the polyphosphoric acid ester that is unexploded [)] is produced by the method for producing IJ phosphate ester, Parts 1 to 6, described below.
For example, 0.48 to 0.48 to 1 mole of dihydric phenols (HOAr, OH,
0°875 mol reaction, then 1.25-2°10
It is obtained by ashing a mole of monohydric phenol (Ar20H), and the acid value of the final polyphosphoric acid ester is adjusted by the amount of monohydric phenol charged.
即ち末端の一部にボスホロクロリデート基ｌ！
（）ＰＣＢ）を残し熱湯による加水分解を行ない所望の
燐酸酸性を持ったポリ燐酸エステルが得られる。That is, a part of the end contains a bosholochloridate group l! () PCB) is left behind and hydrolyzed with hot water to obtain a polyphosphoric acid ester having the desired phosphoric acidity.
次に不発り１に使用されるボＩＪ ％酸エステルの製造
法の例を示すが勿論不発す］はこれらの製造例のみに限
定されるものではない。Next, an example of a method for manufacturing the BoIJ% acid ester used in ``Full 1'' will be shown, but of course ``Full'' is not limited to these production examples.
更に不発１８１！ｌＪは必要に応じて水元１フ−１に使
用のポリ％酸エステルのほかに他の１ハ加ｘ＋」例えば
酸化防止剤、光安定剤、顔料、染料、ｉ、ｊＪ塑剤、そ
の他の難燃剤、補強剤、充填剤、増ｈ１：剤等を添加す
ることができる。Another misfire 181! If necessary, in addition to the poly% acid ester used in the water base 1 fu-1, other ingredients may be added, such as antioxidants, light stabilizers, pigments, dyes, i, jj plastics, and other additives. Flame retardants, reinforcing agents, fillers, h1 thickeners, etc. can be added.
本発明に使用のポリ燐酸エステルの製造法。A method for producing polyphosphoric acid ester used in the present invention.
その１
撹拌棒、コンデンサー、滴下ロート及び扁度計伺フラス
コに
を同時に仕込み窒素気流中１５０℃丑で加熱して２時間
反応させ、ついで滴下ロートよりフレジー／Ｌ／ ２１
０ ｙ（１，９４モ／ｌ／ ）を滴下し、１６０ ヘ１
７０”Ｃで４時間反応させた。Part 1: Charge the stirring bar, condenser, dropping funnel, and flask with an oblimeter at the same time, heat at 150°C in a nitrogen stream, react for 2 hours, and then transfer the flask from the dropping funnel to Freeze/L/21.
Drop 0 y (1,94 mo/l/) and add 160 to 1
The reaction was carried out at 70"C for 4 hours.
反応混合物を熱湯で加水分解した後、触媒及びジエノー
ル類の除去等の精製工程を経て５７０ｙのポリ燐酸エス
テルを得た。この製品をポリ燐酸ニスプール■とする。After hydrolyzing the reaction mixture with hot water, a 570y polyphosphoric acid ester was obtained through purification steps such as removal of the catalyst and dienols. This product is called polyphosphoric acid varnish spool ■.
ポリ燐酸エステル■の品質：黄色液体、平均分子量−５
８４、％１） ＝ ９．９９、酸価＝３．５、ｎ−１の
フェノールとクレゾールとの混合ホスフェートの含量は
３１．５％であった。Quality of polyphosphate ester ■: yellow liquid, average molecular weight -5
84, %1) = 9.99, acid value = 3.5, content of mixed phosphate of n-1 phenol and cresol was 31.5%.
その２
参考例１と同様に反応を行なって、７３０ｙのポリ燐酸
エステルを得た。この製品をポリ燐酸エステル■とする
。Part 2 A reaction was carried out in the same manner as in Reference Example 1 to obtain 730y polyphosphoric acid ester. This product is called polyphosphate ester ■.
ポリ燐酸エステルＨの品質：黄色液体、平均分子ｊｊｊ
−’７８１ 、％Ｐ＝ｌＯ８９、酸価＝４、ｎ−１のト
リフェニルホスフェートの含量１ｄ２０゜１％であった
。Quality of polyphosphoric acid ester H: yellow liquid, average molecule jjj
-'781, %P=lO89, acid value=4, content of n-1 triphenyl phosphate was 1d20°1%.
その３
前記その１と同様の装置をつけたフラスコに所定のオキ
シ垣化鱒とレゾルシン及びフェノール１モルを同時に仕
込み１５０℃捷で反応させ、次いで残部フェノール（６
モル）を反応させた。Part 3: Into a flask equipped with the same equipment as Part 1 above, a specified amount of oxy-cured trout, resorcinol, and 1 mole of phenol were simultaneously charged and reacted at 150°C, and then the remaining phenol (6
mol) were reacted.
反応混合物を水洗後、高４１．（真空下でｎ＝１のトリ
フェニルホス７エートヲ留去し、５１５ｙノホリ鱒酸エ
ステルを得た。この製品をポリ燐酸エステル■とする。After washing the reaction mixture with water, the height was 41. (The n=1 triphenylphos-7ate was distilled off under vacuum to obtain 515y nophoromasic acid ester. This product is referred to as polyphosphoric acid ester (2).
回収トリフェニルホスフェート１ｄ３００ｙであった。The recovered triphenyl phosphate was 1d300y.
ポリ燐酸エステル■の晶質：黄色液体、平均分子量＝
５４０ 、％Ｐ＝１０．６、酸価＝２．２゜ｎ＝１のト
リフェニルホスフェートの含量ハ８％であった−
その４
参名例１七同４＊に反応を行なった。 ９７５ｐのポ
リ燐酸エステルが得うれた。Crystalline of polyphosphoric acid ester ■: Yellow liquid, average molecular weight =
540, %P=10.6, acid value=2.2°, and the content of triphenyl phosphate was 8%. A polyphosphoric acid ester of 975p was obtained.
この製品をポリ燐酸エステル■とする。This product is called polyphosphate ester ■.
ポリ燐酸エステル■の品質：高粘稠な黄褐色液体、平均
分子量−１０１６、％Ｂｒ ＝ ２７．８ 、％Ｐ＝５
．４５、酸価＝５．３．ｎ＝＝ｌの７エニルイソグロビ
ルフエニルの混合ホスフェートの含量は３１％であった
。Quality of polyphosphoric acid ester ■: Highly viscous yellow-brown liquid, average molecular weight -1016, %Br = 27.8, %P = 5
．． 45, acid value = 5.3. The content of mixed phosphate of n==l 7-enyl isoglobylphenyl was 31%.
その５
その１と同様の反応を行ない、６３１ｙのポリ燐酸ニス
デルを得た。Part 5 A reaction similar to Part 1 was carried out to obtain 631y Nisdel polyphosphate.
この製品をポリ燐酸エステル■とする。This product is called polyphosphate ester ■.
ポリ燐酸エステル■の品質：黄色液体、平均分子量＝７
０６、％Ｐ＝８．４、酸価二３．８．ｎ−１のフェノー
ル、クレゾールの混合ホスフェートｉｊ ２５％であっ
た。Quality of polyphosphate ester ■: yellow liquid, average molecular weight = 7
06, %P=8.4, acid value 23.8. n-1 phenol, cresol mixed phosphate ij was 25%.
その６
そのｌと同様に反応を行って９９４７のポリ燐酸エステ
ルを得た。Part 6 The reaction was carried out in the same manner as in Part 1 to obtain 9947 polyphosphoric acid ester.
この製品をポリ燐酸エステル■とする。This product is called polyphosphate ester ■.
ポリ燐酸エステル■の晶質：黄褐色［甜容体、平均分子
量＝１０１５、％Ｐ＝３．９８、％Ｂｒ ＝ ４４．４
ｅ （ｄｌｉ ４．ｓ 、ｎ ＝＝ １のフェノールと
トリグロモ７工ノールとの混合ホスフェートの含量は２
３％であった。Crystalline of polyphosphoric acid ester ■: yellowish brown [tiny form, average molecular weight = 1015, %P = 3.98, %Br = 44.4
e (dli 4.s, the content of mixed phosphate of phenol and triglomonol with n == 1 is 2
It was 3%.
」１記ポリ燐酸エステル■と同■との示差熱熱天秤によ
る加熱減量を測定した結果を第１図に示した。この場合
の温度上昇速度はｌＯ゛Ｃ／分であった。Fig. 1 shows the results of measuring the heating loss of the polyphosphoric acid ester (1) and the polyphosphoric acid ester (2) using a differential thermometer. The temperature increase rate in this case was 10°C/min.
第１図中（ｌａｉｄポリ燐酸エステル（Ｉ）、（２）は
トリフェニルホスフェート、＋３＋はポリ燐酸−ｒ−ス
テル■の加熱減量％曲線である。In FIG. 1, (laid polyphosphoric acid ester (I), (2) is triphenyl phosphate, +3+ is the heating loss % curve of polyphosphoric acid-r-stel (2).
次に上記ポリ燐酸エステル■〜■を使用した本発明の熱
可塑性ｍ脂の難燃化の実施例を示すが本発明は実施例の
みに限定されるものではない。Next, examples of flame retardation of the thermoplastic resin of the present invention using the above-mentioned polyphosphoric acid esters (1) to (2) will be shown, but the present invention is not limited to these examples.
実施例 １
使用原料
゛ポリ（Ｌ６−シメチルー１．４フエニレン）エーテル
６０部※ 部は重量部、以下同様
上記使用原料をミキサーで混合し、３００′Ｃにセント
された射出成型機にて試験片を成形した。Example 1 Raw material used: Poly(L6-dimethyl-1.4phenylene) ether 60 parts* Parts are parts by weight, the same goes for the above raw materials used in a mixer, and a test piece made in an injection molding machine set at 300'C. was molded.
実施例 ２
難燃剤としてポリ燐酸エステル■を１５部使用したほか
は実施例１と同一成分、同一重量部を使用して同様に試
験片を成形した。Example 2 A test piece was molded in the same manner as in Example 1 using the same components and parts by weight, except that 15 parts of polyphosphate ester (2) was used as a flame retardant.
実施例 ３
難燃剤としてポリ燐酸エステル■を１５部使ったほか実
施例１と同一成分、同略−重量部を使用して同様に試験
片を成形した。Example 3 A test piece was molded in the same manner as in Example 1, except that 15 parts of polyphosphate ester (1) was used as a flame retardant, and the same components and approximately - parts by weight as in Example 1 were used.
比較例 １
比較の目的で難燃剤としてトリフェニルホスフェート（
酸価Ｏ，ＯＳ）を１５部使用したほか実施例１と同一成
分、同一重量部を使用して同様に成形した。Comparative Example 1 For comparison purposes, triphenyl phosphate (
It was molded in the same manner as in Example 1, using the same components and parts by weight, except that 15 parts of acid value (O, OS) were used.
第１表にテスト結果を示す。Table 1 shows the test results.
第１表 ポリフェニレン系樹脂のテスト結果ここに
難燃性： ｔｕｂｆ９４の試験法に準じた。各々５個の
試験片に接炎した後の７レーミ
ング（ｆＪａｍｉｎｐ）時間の平均値を示す。Table 1: Test results for polyphenylene resin Flame retardancy: Based on the test method of TUBF94. The average value of 7 laming (fJaminp) times after each 5 test pieces were contacted with flame is shown.
然父形温度：Ｊ工Ｓ、に６７１４に準じた。Natural temperature: According to J Engineering S, 6714.
表面の状慇二成形品のブリードの有無を観察する。2. Observe the surface condition of the molded product for bleeding.
帯電防止性：たばこ試験法に準じた。Antistatic property: According to tobacco test method.
〇−帯電防止性良好 △−帯電防止性やや良 ×−帯電防止性良くない。〇-Good antistatic property △－Slightly good antistatic property ×-Poor antistatic property.
である。It is.
実施例 ４
使用原料
ポリエチレンテレタレート（融点 ２５４℃）
ｌｏｏ部難燃剤、ポリ燐酸エステルｉ
１ｇ部安定剤、トリメチルホスフェート０．３ 部上
記使用原料をミキサーで混合し、常法により紡糸した。Example 4 Raw material used: polyethylene teretalate (melting point: 254°C)
Loo part flame retardant, polyphosphate ester i
1 g part stabilizer, 0.3 part trimethyl phosphate The above raw materials used were mixed in a mixer and spun in a conventional manner.
（紡糸温度＝２８０〜３１０℃）得られた繊維にニード
ルパンチングを施してフェルト状物を作った。(Spinning temperature = 280 to 310°C) The obtained fibers were needle punched to make a felt-like product.
実施例 ５
難燃剤としてポリ燐酸エステル■を１８部使用したほか
実施例４と同一成分、同一重量部を使用して同様に紡糸
した０次にｔ＜ｔ−られた繊維にニードルパンチングを
施してフェルト状物を作った。Example 5 In addition to using 18 parts of polyphosphoric acid ester ■ as a flame retardant, the same components and weight parts as in Example 4 were used, and a zero-order t<t- fiber was spun in the same manner as in Example 4. I made felt-like objects.
実施例 ６
難燃剤としてポリ燐酸エステル■を１８部使用したほか
は実施例−４と同一成分、同一重量部を使用して同様に
紡糸した。Example 6 Spinning was carried out in the same manner as in Example 4 using the same components and parts by weight, except that 18 parts of polyphosphate ester (2) was used as a flame retardant.
次に得゛らｔ′ｔた繊維にニードルパンチングを施して
フェルト状物を作った。Next, the obtained fibers were needle punched to make a felt-like product.
比較例 ２
難燃剤としてトリフェニルホス７エートヲ１８部使用し
たほか実施例４と同一成分、同一重量部を使用して同様
に紡糸した０次に同様フェルト状物を得た。紡糸時のト
リフェニルホスフェートの飛散が認められた。
・
比較例 ３
難燃剤としてテトラブロモビスフェノールＡを１８部イ
匙用したほかは比較例２と同様にした。Comparative Example 2 In addition to using 18 parts of triphenylphos-7ate as a flame retardant, the same components and parts by weight as in Example 4 were used to obtain a zero-order felt-like product which was spun in the same manner as in Example 4. Scattering of triphenyl phosphate was observed during spinning.
- Comparative Example 3 The same procedure as Comparative Example 2 was carried out except that 18 parts of tetrabromobisphenol A was used as a flame retardant.
第２表に実施例４〜６、比較例２及び比較例３のテスト
結果を示す。Table 2 shows the test results of Examples 4 to 6, Comparative Example 2, and Comparative Example 3.
第２表 ポリエステル繊維のテスト結果ここに
難燃性：酸素指数 Ｊ工ＳＤ １２０１耐候性ニアニー
ドメーク−２００時間ｊ１（１射後の布の黄変の度合で
評価した。Table 2 Test results for polyester fibers Flame retardancy: Oxygen index J Engineering SD 1201 Weather Resistance Near Knead Make - 200 hours j1 (Evaluated by the degree of yellowing of the fabric after one shot.
○ 殆んど黄変しない △ わずかに黄変する Ｘ 黄又〜褐色 である。○ Almost no yellowing △ Slight yellowing X Yellow to brown It is.
実施例 ７
使用糸ＰＩ
ナイロン６の粉末 １００部ポリ燐酸ニステ
ルハ・ ２０部上記便川原相をミキサー
で混合し、２７０°Ｃにセントされた射出成型機にて試
験片を成形した。Example 7 Yarn PI used Nylon 6 powder 100 parts Nistelha polyphosphate 20 parts The above-mentioned Fukukawara phase was mixed in a mixer, and a test piece was molded in an injection molding machine set at 270°C.
実施例 ８
実施例 ９
使用原石
ナイロン６６の粉末 １００部ポリ燐酸エス
テル■ 加部
実施例７と同様射出成型機にて試験片を成形した。Example 8 Example 9 Raw nylon 66 powder used: 100 parts polyphosphoric acid ester Addition: A test piece was molded using an injection molding machine in the same manner as in Example 7.
比較例 ４
使用原石
ナイロン６粉末 １００部トリノエニルホ
スフエート ２０部実施例７と同様に射出成型
機にて試験片を成ｊしした。Comparative Example 4 Raw nylon 6 powder used: 100 parts Trinoenyl phosphate: 20 parts A test piece was formed using an injection molding machine in the same manner as in Example 7.
第３表に実施例７〜９及び比較例４のテスト結果を示す
、 実第３表 ナイ
ロンのテスト結果
ここに
難燃性 ：［ＪＬ−９４のテストにｑ”、 Ｌ／た。Table 3 shows the test results of Examples 7 to 9 and Comparative Example 4. Table 3: Test results of nylon Flame retardancy: [JL-94 test: q'', L/.
金型のやけ：難燃剤が成）β中に融解樹脂の表向に浸出
し１浸出した難燃剤が
高温の金型上で分解して焦ける
現象ケ「金型のやけ」という。Mold burn: A phenomenon in which the flame retardant leaches out onto the surface of the molten resin during formation (β) and the leached flame retardant decomposes and burns on the hot mold. This phenomenon is called ``mold burn.''
この様な場合、金型を洗浄する ためにしばしば作条を停止−する 必要がある。In such cases, clean the mold. often stop cropping for There is a need.
〇−金型のやけなし ×−金型のやけあり である。〇-No mold damage ×− There is some mold burnt. It is.
比例 １０
使用原料
上記席料をミキサーで混合り、 １８０℃に加熱した
射出成型機で試験片を成形した。Proportion 10 Raw Materials Used The above ingredients were mixed in a mixer, and a test piece was molded in an injection molding machine heated to 180°C.
失厩例 １１
難燃剤としてポリ燐酸エステル■の代りにポリ燐酸エス
テル■を５部使用したほかは実施例１０と同一成分、同
一重量部を使用して同様に試験片を成）ヒした。Loss example 11 A test piece was prepared in the same manner as in Example 10 using the same components and parts by weight, except that 5 parts of polyphosphate ester (2) was used instead of polyphosphate ester (2) as a flame retardant.
比リウこ例 ５ １吏月Ｊ川ミ刺１ 実施例１０と同様に試験片を作成した。Example 5 1 Rizuki J River Misashi 1 A test piece was prepared in the same manner as in Example 10.
テスト結果を第４表に示した。The test results are shown in Table 4.
第１図及び％１、第２、第３、第４表に示したごとく、
本発明に使用のボＩＪ ％酸エステルは熱可塑性イ舅脂
に難燃性を付与するばかシでなく、従来の難燃剤に比較
して揮発性、耐熱性、耐候性、移行性、帯電防止性、金
型のやけ等にガミてすぐれた難燃剤であることがわかる
。As shown in Figure 1 and Tables %1, 2, 3, and 4,
The BoIJ% acid ester used in the present invention does not impart flame retardancy to thermoplastic resin, but has higher volatility, heat resistance, weather resistance, migration properties, and antistatic properties compared to conventional flame retardants. It can be seen that it is an excellent flame retardant with good resistance to heat and mold burns.
第１図は示差熱天秤によるポリ燐酸エステル（Ｉ）、同
ωυ及ヒトリノエニルホス７エー １〜の加熱減量（％
）と温度（℃）との関係を示す図である。
１、 ポリ燐酸エステルエの温度によるΔ日熱；斌量曲
線
２゜ トリフェニルホスフェートの温度による加熱減量
曲線
３、 ポリ燐酸エステル■の温度による加熱減量曲線。
特許出願人 株式会社犬八化学工業所Figure 1 shows the heating loss (%) of polyphosphoric acid ester (I), polyphosphoric acid ester (I), polyphosphoric acid ωυ, and human trinoenylphos 7A 1~ as measured by differential thermal balance.
) and temperature (°C). 1. ∆day heat due to temperature of polyphosphoric acid ester; Disposal curve 2゜ Heat loss curve due to temperature of triphenyl phosphate 3. Heat loss curve depending on temperature of polyphosphoric acid ester ■. Patent applicant: Inuhachi Chemical Industry Co., Ltd.
Claims (1)
価の７コ一ノールｍ及びＡｒ２０Ｈで表わされる一価の
フェノール類との反応によって得られるポリ崎酸エステ
ルにして該ポリ燐酸エステルのｎ量体のｎ（ｎは１以上
の整数で、分子中の焙ｊ京子の個′＃、を表わす）が１
〜１５の整数の混合物てあり、ｎ−１の成分を４０重量
％以下含有し、かつ酸価が１５以下のポリ燐酸エステル
を主成分として５〜３０重量％含旬してなる難燃性熱＋
ＪＪ塑性イ☆１脂組成物。 ここにＡｒｔ、Ａｒ２は夫々間−又は相異なる芳香族基
を示す。 ２ ポリ燐酸エステルが直鎮状と枝わかれ状との構造式
をもった混合ポリ燐酸エステルである特許請求の範囲第
１項記載の難燃性熟町塑性々６（脂組成物。 ３２価のフェノール類がハイドロキノン、レゾルシノー
ル、ビスフェノールＡ１ ビスフェノールＦ１ ビスフ
ェノールＳ１これらの塩素化物、又はこれらの臭素化物
の群から選ばれた化合物の一種以上であり、−価のフェ
ノール類が７エ／−ル、クレゾール、キシレノール、イ
ンプロピルフェノール、グチルフェノール又はこれらの
塩素化物又はこれらの臭素化物の群から選ばれた一種以
」二である特許請求の範囲 塑性樹脂組成物。 ４ 熱可塑性樹脂がポリフェニレンエーテル系樹脂、ポ
リエステル系樹脂、ボリアミド系樹月旨、ポリカーボネ
ート糸牢尉月旨又はポリオレフイン系＋Ａ脂である特許
Ｈ］−求の範囲第１項又は第２項記載の難燃性熱可塑性
樹脂組成物。[Claims] 1. 2 represented by 1. chloride and HOAr 10 H
A polysilicate ester obtained by reaction with monovalent phenols represented by heptaconol m and Ar20H, and n of the n-mer of the polyphosphoric acid ester (n is an integer of 1 or more; , which represents Kyoko's number) is 1
A flame-retardant heat-retardant which is a mixture of integers of ~15, contains 40% by weight or less of component n-1, and contains 5-30% by weight of a polyphosphoric acid ester with an acid value of 15 or less as a main component. +
JJ Plastic A☆1 fat composition. Here, Art and Ar2 each represent an aromatic group or a different aromatic group. 2. The flame-retardant Jukumachi Plastics 6 (fatty composition) according to claim 1, wherein the polyphosphoric acid ester is a mixed polyphosphoric acid ester having a straight structure and a branched structure. The phenols are one or more compounds selected from the group of hydroquinone, resorcinol, bisphenol A1, bisphenol F1, bisphenol S1, chlorinated products of these, or brominated products of these, and the -valent phenols are 7 ethyl, cresol, Claimed plastic resin composition which is one or more selected from the group of xylenol, inpropylphenol, butylphenol, chlorinated products thereof, or brominated products thereof. 4. The thermoplastic resin is polyphenylene ether resin, polyester. The flame-retardant thermoplastic resin composition according to claim 1 or 2, which is a polyamide resin, a polycarbonate resin, or a polyolefin + A resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7809283A JPS59202240A (en) | 1983-05-02 | 1983-05-02 | Flame-retardant thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7809283A JPS59202240A (en) | 1983-05-02 | 1983-05-02 | Flame-retardant thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59202240A true JPS59202240A (en) | 1984-11-16 |
| JPS6225706B2 JPS6225706B2 (en) | 1987-06-04 |
Family
ID=13652211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7809283A Granted JPS59202240A (en) | 1983-05-02 | 1983-05-02 | Flame-retardant thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59202240A (en) |
Cited By (55)
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| JPH01203468A (en) * | 1988-02-10 | 1989-08-16 | Marubishi Yuka Kogyo Kk | Flame-retardant synthetic resin composition |
| JPH02115262A (en) * | 1988-09-22 | 1990-04-27 | General Electric Co <Ge> | Polymer mixture containing aromatic polycarbonate, styrene copolymer and/or graft polymer, and flame retardant, and molded article of said polymer mixture |
| US5122556A (en) * | 1990-04-23 | 1992-06-16 | General Electric Company | Tetra (lower alkaryl) p-phenylene diphosphate-polycarbonate blends |
| US5194581A (en) * | 1989-03-09 | 1993-03-16 | Leong Kam W | Biodegradable poly(phosphoesters) |
| US5204394A (en) * | 1988-09-22 | 1993-04-20 | General Electric Company | Polymer mixture having aromatic polycarbonate, styrene I containing copolymer and/or graft polymer and a flame-retardant, articles formed therefrom |
| JPH05186681A (en) * | 1992-01-16 | 1993-07-27 | Asahi Chem Ind Co Ltd | Flame-retardant polyphenylene ether resin composition |
| US5309261A (en) * | 1991-07-03 | 1994-05-03 | Goldstar Co., Ltd. | Optical system for laser beam scanner |
| JPH0753876A (en) * | 1992-08-06 | 1995-02-28 | Asahi Chem Ind Co Ltd | Resin composition |
| EP0640655A2 (en) * | 1993-08-26 | 1995-03-01 | Bayer Ag | Flame-retardant, stress crack resistant polycarbonate ABS moulding composition |
| WO1996011977A1 (en) * | 1994-10-13 | 1996-04-25 | Akzo Nobel N.V. | Polycarbonate-containing polymers flame retarded with oligomeric phosphate esters |
| EP0761746A1 (en) | 1995-08-17 | 1997-03-12 | Bayer Ag | Ultrafine inorganic powders as flame retardants in thermoplastic moulding compositions |
| US5627228A (en) * | 1994-05-10 | 1997-05-06 | Daicel Chemical Industries, Ltd. | Flame-retardant resin composition |
| US5663280A (en) * | 1995-10-23 | 1997-09-02 | The Dow Chemical Company | Carbonate polymer resins containing low volatility aromatic phosphate ester compounds |
| USRE36188E (en) * | 1989-09-20 | 1999-04-06 | General Electric Company | Polymer mixture having aromatic polycarbonate styrene I containing copolymer and/or graft polymer and a flame-retardant, articles formed therefrom |
| US6096821A (en) * | 1999-04-02 | 2000-08-01 | General Electric Company | Polyphenylene ether resin concentrates |
| US6258881B1 (en) | 1998-10-07 | 2001-07-10 | Sumitomo Chemical Company, Limited | Polyphenylene ether resin composition |
| US6319432B1 (en) | 1999-06-11 | 2001-11-20 | Albemarle Corporation | Bisphenol-A bis(diphenyl phosphate)-based flame retardant |
| US6322882B1 (en) | 1998-10-14 | 2001-11-27 | Sumitomo Chemical Company, Limited | Polyphenylene ether resin composition |
| US6359043B1 (en) | 1998-09-24 | 2002-03-19 | General Electric Company | Mica as flame retardant in glass filled noryl |
| JP2002161211A (en) * | 2000-11-24 | 2002-06-04 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
| US6399685B1 (en) | 2000-12-11 | 2002-06-04 | Albemarle Corporation | Purification of arylene polyphosphate esters |
| US6437029B1 (en) | 2000-10-31 | 2002-08-20 | Cheil Industries Inc. | Flame retardant polycarbonate resin composition |
| US6469077B1 (en) | 1998-10-13 | 2002-10-22 | Sumitomo Chemical Company Limited | Polyphenylene ether resin composition |
| US6569930B1 (en) | 1997-08-11 | 2003-05-27 | Bayer Aktiengesellschaft | Flame and stress crack resistant polycarbonate molding compositions |
| US6590015B1 (en) * | 1992-10-22 | 2003-07-08 | Bayer Aktiengesellschaft | Flame-resistant molding compounds |
| US6706788B2 (en) | 1997-05-23 | 2004-03-16 | Bayer Aktiengesellschaft | Flame-resistant polycarbonate moulding materials which are dimensionally stable at high temperatures and have high flow line strength |
| US6727301B1 (en) | 1999-03-27 | 2004-04-27 | Bayer Aktiengesellschaft | Flame-resistant, impact-resistant modified polycarbonate molding and extrusion masses |
| US6767943B1 (en) | 1999-03-27 | 2004-07-27 | Bayer Aktiengesellschaft | Flame-resistant polycarbonate moulding materials modified with graft polymers |
| US6797784B1 (en) | 1998-11-10 | 2004-09-28 | Bayer Aktiengesellschaft | Thermoplastic resins with a low proportion of coarse particles |
| US6815476B1 (en) | 1995-06-07 | 2004-11-09 | General Electric Company | Phosphate flame retardant polymers |
| US7094818B2 (en) | 2001-09-03 | 2006-08-22 | Cheil Industries, Inc. | Thermoplastic resin compositions containing mixtures of cyclic phosphazenes and phosphoric acid esters |
| JP2006328174A (en) * | 2005-05-25 | 2006-12-07 | Jsr Corp | Cyclic olefin resin composition and its molded item |
| JP2006328175A (en) * | 2005-05-25 | 2006-12-07 | Jsr Corp | Cyclic olefin resin composition and its molded item |
| US7196130B2 (en) | 2002-06-14 | 2007-03-27 | Mitsui Chemicals, Inc. | Thermoplastic resin composition, polymer composition, and molded product comprising the composition |
| US7235598B1 (en) | 1999-02-04 | 2007-06-26 | Bayer Materialscience Ag | Polycarbonate moulding materials with anti-static properties |
| US7319116B2 (en) | 2002-08-05 | 2008-01-15 | Bayer Materialscience Ag | Flame-resistant polycarbonate molding composition modified with a graft polymer |
| US7498370B2 (en) | 2002-07-08 | 2009-03-03 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition |
| US7511088B2 (en) | 2002-07-11 | 2009-03-31 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition |
| US7569629B2 (en) | 2004-12-30 | 2009-08-04 | Cheil Industries Inc. | Flame retardant polycarbonate resin composition |
| WO2010010669A1 (en) | 2008-07-21 | 2010-01-28 | 三菱エンジニアリングプラスチックス株式会社 | Flame-retardant polybutylene terephthalate-based resin composition |
| US7659332B2 (en) | 2005-12-30 | 2010-02-09 | Cheil Industries Inc. | Flame retardant polycarbonate thermoplastic resin composition having good extrusion moldability and impact resistance |
| US8119726B2 (en) | 2004-10-13 | 2012-02-21 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition |
| WO2013157345A1 (en) | 2012-04-20 | 2013-10-24 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition |
| KR20140050149A (en) | 2012-10-17 | 2014-04-29 | 에스케이씨 주식회사 | Flame retardant with network structure and preparation method thereof |
| US8901218B2 (en) | 2007-12-18 | 2014-12-02 | Cheil Industries Inc. | Branched (meth)acrylate copolymer with high refractive index and method for preparing the same |
| US8940836B2 (en) | 2008-12-17 | 2015-01-27 | Cheil Industries Inc. | Polycarbonate resin composition with improved transparency and scratch-resistance |
| US9353260B2 (en) | 2013-04-19 | 2016-05-31 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition and molded article |
| US9365671B2 (en) | 2013-12-04 | 2016-06-14 | Samsung Sdi Co., Ltd. | Styrene-based copolymer and thermoplastic resin composition including the same |
| WO2016197915A1 (en) * | 2015-06-08 | 2016-12-15 | 金发科技股份有限公司 | Polycarbonate composition and preparation method therefor |
| US9790362B2 (en) | 2014-06-27 | 2017-10-17 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and molded article made using the same |
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| US9856371B2 (en) | 2014-06-27 | 2018-01-02 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and low-gloss molded article made therefrom |
| US9862822B2 (en) | 2014-11-18 | 2018-01-09 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and molded article made using the same |
| US9902850B2 (en) | 2014-06-26 | 2018-02-27 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition |
| US10640624B2 (en) | 2016-12-22 | 2020-05-05 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article using the same |
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| JP5214099B2 (en) | 2005-09-28 | 2013-06-19 | ウィンテックポリマー株式会社 | Flame retardant polybutylene terephthalate resin composition |
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|---|---|---|---|---|
| GB787356A (en) * | 1955-03-29 | 1957-12-04 | British Cellophane Ltd | Improvements in or relating to the manufacture of articles comprising ethylene polymer |
| JPS5432818A (en) * | 1977-08-19 | 1979-03-10 | Nippon Kokan Kk <Nkk> | Anti-corrosion coating process for pipe joint part |
| JPS55118957A (en) * | 1979-03-02 | 1980-09-12 | Gen Electric | Flameeproof composition |
| JPS5667253A (en) * | 1979-10-19 | 1981-06-06 | Ici Ltd | Manufacture of thermoplastic film molecularroriented |
| JPS57207641A (en) * | 1981-06-17 | 1982-12-20 | Adeka Argus Chem Co Ltd | Flame-retardant polyphenylene ether resin composition |
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1983
- 1983-05-02 JP JP7809283A patent/JPS59202240A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB787356A (en) * | 1955-03-29 | 1957-12-04 | British Cellophane Ltd | Improvements in or relating to the manufacture of articles comprising ethylene polymer |
| JPS5432818A (en) * | 1977-08-19 | 1979-03-10 | Nippon Kokan Kk <Nkk> | Anti-corrosion coating process for pipe joint part |
| JPS55118957A (en) * | 1979-03-02 | 1980-09-12 | Gen Electric | Flameeproof composition |
| JPS5667253A (en) * | 1979-10-19 | 1981-06-06 | Ici Ltd | Manufacture of thermoplastic film molecularroriented |
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Cited By (62)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01203468A (en) * | 1988-02-10 | 1989-08-16 | Marubishi Yuka Kogyo Kk | Flame-retardant synthetic resin composition |
| JPH02115262A (en) * | 1988-09-22 | 1990-04-27 | General Electric Co <Ge> | Polymer mixture containing aromatic polycarbonate, styrene copolymer and/or graft polymer, and flame retardant, and molded article of said polymer mixture |
| US5204394A (en) * | 1988-09-22 | 1993-04-20 | General Electric Company | Polymer mixture having aromatic polycarbonate, styrene I containing copolymer and/or graft polymer and a flame-retardant, articles formed therefrom |
| US5194581A (en) * | 1989-03-09 | 1993-03-16 | Leong Kam W | Biodegradable poly(phosphoesters) |
| USRE36188E (en) * | 1989-09-20 | 1999-04-06 | General Electric Company | Polymer mixture having aromatic polycarbonate styrene I containing copolymer and/or graft polymer and a flame-retardant, articles formed therefrom |
| US5122556A (en) * | 1990-04-23 | 1992-06-16 | General Electric Company | Tetra (lower alkaryl) p-phenylene diphosphate-polycarbonate blends |
| US5309261A (en) * | 1991-07-03 | 1994-05-03 | Goldstar Co., Ltd. | Optical system for laser beam scanner |
| JPH05186681A (en) * | 1992-01-16 | 1993-07-27 | Asahi Chem Ind Co Ltd | Flame-retardant polyphenylene ether resin composition |
| JPH0753876A (en) * | 1992-08-06 | 1995-02-28 | Asahi Chem Ind Co Ltd | Resin composition |
| US6590015B1 (en) * | 1992-10-22 | 2003-07-08 | Bayer Aktiengesellschaft | Flame-resistant molding compounds |
| EP0640655A2 (en) * | 1993-08-26 | 1995-03-01 | Bayer Ag | Flame-retardant, stress crack resistant polycarbonate ABS moulding composition |
| EP0640655A3 (en) * | 1993-08-26 | 1995-05-24 | Bayer Ag | Flame-retardant, stress crack resistant polycarbonate ABS moulding composition. |
| US5627228A (en) * | 1994-05-10 | 1997-05-06 | Daicel Chemical Industries, Ltd. | Flame-retardant resin composition |
| US6022917A (en) * | 1994-05-10 | 2000-02-08 | Daicel Chemical Industries, Ltd. | Flame-retardant resin composition |
| US5994433A (en) * | 1994-05-10 | 1999-11-30 | Daicel Chemical Industries, Ltd. | Flame-retardant resin composition |
| WO1996011977A1 (en) * | 1994-10-13 | 1996-04-25 | Akzo Nobel N.V. | Polycarbonate-containing polymers flame retarded with oligomeric phosphate esters |
| US6815476B1 (en) | 1995-06-07 | 2004-11-09 | General Electric Company | Phosphate flame retardant polymers |
| EP0761746A1 (en) | 1995-08-17 | 1997-03-12 | Bayer Ag | Ultrafine inorganic powders as flame retardants in thermoplastic moulding compositions |
| US5663280A (en) * | 1995-10-23 | 1997-09-02 | The Dow Chemical Company | Carbonate polymer resins containing low volatility aromatic phosphate ester compounds |
| US6706788B2 (en) | 1997-05-23 | 2004-03-16 | Bayer Aktiengesellschaft | Flame-resistant polycarbonate moulding materials which are dimensionally stable at high temperatures and have high flow line strength |
| US6569930B1 (en) | 1997-08-11 | 2003-05-27 | Bayer Aktiengesellschaft | Flame and stress crack resistant polycarbonate molding compositions |
| US6359043B1 (en) | 1998-09-24 | 2002-03-19 | General Electric Company | Mica as flame retardant in glass filled noryl |
| US6258881B1 (en) | 1998-10-07 | 2001-07-10 | Sumitomo Chemical Company, Limited | Polyphenylene ether resin composition |
| US6469077B1 (en) | 1998-10-13 | 2002-10-22 | Sumitomo Chemical Company Limited | Polyphenylene ether resin composition |
| US6322882B1 (en) | 1998-10-14 | 2001-11-27 | Sumitomo Chemical Company, Limited | Polyphenylene ether resin composition |
| US6797784B1 (en) | 1998-11-10 | 2004-09-28 | Bayer Aktiengesellschaft | Thermoplastic resins with a low proportion of coarse particles |
| US7235598B1 (en) | 1999-02-04 | 2007-06-26 | Bayer Materialscience Ag | Polycarbonate moulding materials with anti-static properties |
| US6727301B1 (en) | 1999-03-27 | 2004-04-27 | Bayer Aktiengesellschaft | Flame-resistant, impact-resistant modified polycarbonate molding and extrusion masses |
| US6767943B1 (en) | 1999-03-27 | 2004-07-27 | Bayer Aktiengesellschaft | Flame-resistant polycarbonate moulding materials modified with graft polymers |
| US6096821A (en) * | 1999-04-02 | 2000-08-01 | General Electric Company | Polyphenylene ether resin concentrates |
| US6319432B1 (en) | 1999-06-11 | 2001-11-20 | Albemarle Corporation | Bisphenol-A bis(diphenyl phosphate)-based flame retardant |
| US6900256B2 (en) | 2000-10-31 | 2005-05-31 | Cheil Industries Inc. | Thermoplastic resin compositions containing polyphosphate ester morpholides as flame retardants |
| US6437029B1 (en) | 2000-10-31 | 2002-08-20 | Cheil Industries Inc. | Flame retardant polycarbonate resin composition |
| US6576161B2 (en) | 2000-10-31 | 2003-06-10 | Cheil Industries, Inc. | Polyphosphate ester morpholides, mixtures thereof, and thermoplastic resin compositions containing polyphosphate ester morpholides as flame retardants |
| JP2002161211A (en) * | 2000-11-24 | 2002-06-04 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
| US6399685B1 (en) | 2000-12-11 | 2002-06-04 | Albemarle Corporation | Purification of arylene polyphosphate esters |
| US7094818B2 (en) | 2001-09-03 | 2006-08-22 | Cheil Industries, Inc. | Thermoplastic resin compositions containing mixtures of cyclic phosphazenes and phosphoric acid esters |
| US7196130B2 (en) | 2002-06-14 | 2007-03-27 | Mitsui Chemicals, Inc. | Thermoplastic resin composition, polymer composition, and molded product comprising the composition |
| EP1911802A2 (en) | 2002-06-14 | 2008-04-16 | Mitsui Chemicals, Inc. | Thermoplastic resin composition, polymer composition, and molded object obtained from the composition |
| US7498370B2 (en) | 2002-07-08 | 2009-03-03 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition |
| US7511088B2 (en) | 2002-07-11 | 2009-03-31 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition |
| US7319116B2 (en) | 2002-08-05 | 2008-01-15 | Bayer Materialscience Ag | Flame-resistant polycarbonate molding composition modified with a graft polymer |
| US8119726B2 (en) | 2004-10-13 | 2012-02-21 | Cheil Industries Inc. | Flame retardant thermoplastic resin composition |
| US7569629B2 (en) | 2004-12-30 | 2009-08-04 | Cheil Industries Inc. | Flame retardant polycarbonate resin composition |
| JP2006328174A (en) * | 2005-05-25 | 2006-12-07 | Jsr Corp | Cyclic olefin resin composition and its molded item |
| JP2006328175A (en) * | 2005-05-25 | 2006-12-07 | Jsr Corp | Cyclic olefin resin composition and its molded item |
| US7659332B2 (en) | 2005-12-30 | 2010-02-09 | Cheil Industries Inc. | Flame retardant polycarbonate thermoplastic resin composition having good extrusion moldability and impact resistance |
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| WO2010010669A1 (en) | 2008-07-21 | 2010-01-28 | 三菱エンジニアリングプラスチックス株式会社 | Flame-retardant polybutylene terephthalate-based resin composition |
| US8940836B2 (en) | 2008-12-17 | 2015-01-27 | Cheil Industries Inc. | Polycarbonate resin composition with improved transparency and scratch-resistance |
| US9499695B2 (en) | 2012-04-20 | 2016-11-22 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition |
| WO2013157345A1 (en) | 2012-04-20 | 2013-10-24 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition |
| KR20140050149A (en) | 2012-10-17 | 2014-04-29 | 에스케이씨 주식회사 | Flame retardant with network structure and preparation method thereof |
| US9353260B2 (en) | 2013-04-19 | 2016-05-31 | Mitsubishi Engineering-Plastics Corporation | Polycarbonate resin composition and molded article |
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| US9850333B2 (en) | 2014-06-27 | 2017-12-26 | Lotte Advanced Materials Co., Ltd. | Copolymers and thermoplastic resin composition including the same |
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| US9862822B2 (en) | 2014-11-18 | 2018-01-09 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and molded article made using the same |
| WO2016197915A1 (en) * | 2015-06-08 | 2016-12-15 | 金发科技股份有限公司 | Polycarbonate composition and preparation method therefor |
| US10640624B2 (en) | 2016-12-22 | 2020-05-05 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition and article using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6225706B2 (en) | 1987-06-04 |
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