JPS60206845A - Expandable thermoplastic copolymer particle - Google Patents
Expandable thermoplastic copolymer particleInfo
- Publication number
- JPS60206845A JPS60206845A JP6462884A JP6462884A JPS60206845A JP S60206845 A JPS60206845 A JP S60206845A JP 6462884 A JP6462884 A JP 6462884A JP 6462884 A JP6462884 A JP 6462884A JP S60206845 A JPS60206845 A JP S60206845A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- flame retardant
- copolymer particles
- expandable thermoplastic
- thermoplastic copolymer
- Prior art date
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Abstract
Description
【発明の詳細な説明】
本発明は、難燃性・耐熱性に優れ、かつ発泡性・成形性
の良好な発泡性熱可塑性樹脂粒子に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to expandable thermoplastic resin particles that have excellent flame retardancy and heat resistance, as well as good foamability and moldability.
発泡性合成樹脂粒子としては、発泡性ポリスチレン樹脂
粒子がよく知られており、該粒子を用いることによって
安価で容易に型発泡成形体を得ることができる。しかし
ながら該発泡成形体は、重合物を構成する単量体がスチ
レンであるだめ比較的温度の高い配管の保温材、屋根用
断熱材、自動車部材、ソーラーシステム用保温材等の耐
熱性を要求される用途には使用できない欠点がある。As expandable synthetic resin particles, expandable polystyrene resin particles are well known, and by using these particles, a molded foamed article can be easily obtained at low cost. However, since the monomer constituting the polymer is styrene, the foamed molded product is required to have heat resistance for use as a heat insulating material for relatively high-temperature pipes, roof heat insulating materials, automobile parts, solar system heat insulating materials, etc. There is a drawback that it cannot be used for other purposes.
この為、本発明者らは、実用性に於て充分な耐熱性を有
する発泡性熱可塑性共重合体粒子を得るには、重合体を
構成する単量体組成としては、アルファメチルメチレフ
１０重ｉ％以上、かつアクリロニ） ＩＪル５重量％以
上を含有してなる共重合体粒子を得、この樹脂粒子に易
揮発性発泡剤を含浸せしめる必要があると考えた。For this reason, the present inventors have determined that in order to obtain expandable thermoplastic copolymer particles having sufficient heat resistance for practical use, the monomer composition constituting the polymer should be alpha methyl methyl ref 10 It was considered necessary to obtain copolymer particles containing at least 5% by weight of acrylonitrile and at least 5% by weight of acrylonitrile, and to impregnate these resin particles with an easily volatile blowing agent.
しかして、更にかかる耐熱性を有する発泡性熱可塑性共
重合体粒子に難燃剤を加えＮ燃性を付与しようと試みた
が、共重合体を構成する単量体の特性に起因して、この
発泡性熱可塑性共重合体粒子に難燃性を付与することは
非常に困難であり、従来、発泡スチレン系樹脂に用いら
れている各種の難燃剤を用いた場合、満足すべき難燃性
は全く得られないか、又は非常に多量の難燃剤を用いて
難燃性を向」ニさせると耐熱性及び成形性の著しく劣っ
たものになってしまった。かかる観点に立って、本発明
者らは鋭意研究した結果、アルファメチルスチレンーア
クリロニ） ＩＪル系共重合体粒子に、特定の難燃剤と
、好ましくは特定の難燃助剤とを含有せしめ、該粒子に
易揮発性発泡剤を含浸せしめることによシ、耐熱性、難
燃性及び成形性に優れた発泡性熱可塑性共重合体粒子が
得られることを見い出し、本発明をなすに到った。すな
わち本発明は、重合体を構成する単量体組成が、アルフ
ァメチルスチレン１０〜８０重量％、アクリロニトリル
５〜５０重量％、更にスチレン、クロルスチレン、パラ
メチルスチレン、ｔ−ブチルスチレン、ｔ−アクリル酸
エステル、メタクリル酸エステルから選ばれた少なくと
も１種の化合物０〜７０重量％であり、易揮発性発泡剤
２〜１５重量％及び分解温度が１８０〜２５０ ’Ｃの
難燃剤１〜１５重量％と、１時間半減期温度が１５０〜
２５０℃の難燃助剤０２〜２重量％を含有してなる発泡
性熱可塑性共重合体粒子である。However, attempts were made to add a flame retardant to the expandable thermoplastic copolymer particles having such heat resistance, but due to the characteristics of the monomers constituting the copolymer, this It is extremely difficult to impart flame retardancy to expandable thermoplastic copolymer particles, and when using the various flame retardants conventionally used in expanded styrene resins, satisfactory flame retardance has not been achieved. If no flame retardant was obtained or a very large amount of flame retardant was used to improve flame retardancy, the result was a product with significantly inferior heat resistance and moldability. From this point of view, as a result of intensive research, the present inventors have found that the alpha methylstyrene-acrylon copolymer particles contain a specific flame retardant and preferably a specific flame retardant aid. discovered that expandable thermoplastic copolymer particles having excellent heat resistance, flame retardance, and moldability can be obtained by impregnating the particles with an easily volatile blowing agent, and have accomplished the present invention. It was. That is, in the present invention, the monomer composition constituting the polymer is 10 to 80% by weight of alpha methylstyrene, 5 to 50% by weight of acrylonitrile, and further includes styrene, chlorostyrene, paramethylstyrene, t-butylstyrene, and t-acrylic. 0 to 70% by weight of at least one compound selected from acid esters and methacrylic esters, 2 to 15% by weight of easily volatile foaming agents, and 1 to 15% by weight of flame retardants with a decomposition temperature of 180 to 250'C. And the 1 hour half-life temperature is 150 ~
These are expandable thermoplastic copolymer particles containing 02 to 2% by weight of a flame retardant aid at 250°C.
本発明に使用されるアルファメチルスチレンの量は、１
０〜８０重量％の範囲で所望する耐熱性と発泡倍率によ
って決められるが、１０重量％未満であると耐熱性向上
の効果が見られなくなり、８０重量％を越えると重合転
化率が低下し、樹脂中に多量の単量体が残って耐熱性が
悪化する。５０倍発発泡形体で１００℃の耐熱性ヲ得る
為にはアルファメチルスチレン２０〜５０重量％を用い
る必要があり、５〜１０倍発泡成形体で１１０℃の耐熱
性を得る為には５０〜８０重量％のアルファメチルスチ
レンを用いる必要がある。The amount of alpha methylstyrene used in the present invention is 1
It is determined in the range of 0 to 80% by weight depending on the desired heat resistance and expansion ratio, but if it is less than 10% by weight, the effect of improving heat resistance will not be seen, and if it exceeds 80% by weight, the polymerization conversion rate will decrease. A large amount of monomer remains in the resin, resulting in poor heat resistance. In order to obtain a heat resistance of 100°C in a 50 times foamed product, it is necessary to use 20 to 50% by weight of alpha methylstyrene, and in order to obtain a heat resistance of 110°C in a 5 to 10 times foamed product, it is necessary to use 50 to 50% by weight. It is necessary to use 80% by weight alpha methylstyrene.
又、本発明に使用されるアクリロニトリルは、組成物の
重合転化率を向上させる為に必要であシ、５重量％以下
では組成物の重合転化率が低くなり好ましくない。また
５０重量％以上用いても重合転化率は変らず、樹脂が黄
襖色に着色するので好ましくない。Further, acrylonitrile used in the present invention is necessary to improve the polymerization conversion rate of the composition, and if it is less than 5% by weight, the polymerization conversion rate of the composition will decrease, which is not preferable. Further, even if it is used in an amount of 50% by weight or more, the polymerization conversion rate does not change and the resin is colored yellow, which is not preferable.
アルファメチルスチレン及びアクリロニトリル以外の単
量体としては、スチレン、クロルスチレン、パラメチル
スチレン、ｔ−ブチルスチレン等の各種置換スチレン、
メチルアクリレート、エチルアクリレート、ブチルアク
リレート等のアクリル酸エステル、メチルメタクリレー
ト、エチルメタクリレート、ブチルアクリレート等のメ
タクリル酸エステルの中の１種又は２種以上を適宜用い
ることができる。Monomers other than alpha-methylstyrene and acrylonitrile include various substituted styrenes such as styrene, chlorostyrene, para-methylstyrene, and t-butylstyrene;
One or more of acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, and methacrylic esters such as methyl methacrylate, ethyl methacrylate, and butyl acrylate can be used as appropriate.
本発明に用いられる易揮発性発泡剤としては、プロパン
、ブタン、ペンタン等の脂肪族炭化水素；シクロブタン
、シクロペンタン、シクロヘキサン等の環式脂肪族灰化
水素及びトリクロルフルオルメタン、ジクロルフルオル
メタン、ジクロルフルオルメタン、メチルクロライド、
ジクロルテトラフルオルエタン、エチルクロライド等の
ハロゲン化炭化水素があげられる。これら発泡剤の用い
られるべき量は、所望する発泡成形体の発泡倍率によっ
て異なるが、２重量％から１５重量％を含有せしむるこ
とにより２倍から１００倍の発泡成形体を得ることが可
能である。Easily volatile blowing agents used in the present invention include aliphatic hydrocarbons such as propane, butane, and pentane; cycloaliphatic hydrogen ash such as cyclobutane, cyclopentane, and cyclohexane, and trichlorofluoromethane and dichlorofluorocarbons. Methane, dichlorofluoromethane, methyl chloride,
Examples include halogenated hydrocarbons such as dichlorotetrafluoroethane and ethyl chloride. The amount of these blowing agents to be used varies depending on the desired expansion ratio of the foamed molded product, but by containing 2 to 15% by weight, it is possible to obtain a foamed molded product that is 2 times to 100 times larger. It is.
本発明に於て用いる難燃剤は、上記粒子に難燃性を付与
する目的で用いられるが、少量で良好な難燃性を発揮さ
せ、かっ耐熱性、成形性を悪化させない難燃剤として、
分解温度が１８０〜２５０″Ｃのものであることが必要
であり、好ましくは難燃剤の融点が８０′ｃ以上のもの
である。このような難燃剤としてはハロゲン糸難燃剤が
あり、ヘキサブロムシクロドデカン、テトラブロムビス
フェノールＡ及びそのジアリルエーテル、モノクロルペ
ンタブロムシクロヘキサンなどを始めとして多くの難燃
剤があげられるが、中でもヘキサブロムシクロドデカン
が好ましい。難燃剤の使用量は１〜１５重量％、好まし
くは３〜１０重量％である。使用量が１重量％未満であ
ると難燃性を付与することが困難であり、１５重量％を
こえて用いると耐熱性、成形性が著しく劣ったものしか
得られなくなる。The flame retardant used in the present invention is used for the purpose of imparting flame retardancy to the particles, and as a flame retardant that exhibits good flame retardancy in a small amount and does not deteriorate heat resistance or moldability,
It is necessary that the decomposition temperature is 180 to 250"C, and preferably the melting point of the flame retardant is 80"C or higher.Such flame retardants include halogen thread flame retardants, such as hexabromide There are many flame retardants including cyclododecane, tetrabromobisphenol A and its diallyl ether, monochloropentabromocyclohexane, etc., but among them, hexabromocyclododecane is preferred.The amount of flame retardant used is preferably 1 to 15% by weight. is 3 to 10% by weight.If the amount used is less than 1% by weight, it will be difficult to impart flame retardancy, and if it is used in excess of 15% by weight, the product will have extremely poor heat resistance and moldability. You won't be able to get it.
しかして、これらの難燃剤に、少量の難燃助剤を併用す
ることにより著しい難燃性の向上が′見られる。このよ
うな目的で使用される難燃助剤としては、一般に過酸化
物等のラジカル発生剤が用いられるが、本発明において
難燃性を発揮させるのに好ましい難燃助剤としては、１
時間半減期温度が１５０〜２５０″Ｃのものであり、特
に下記の式（Ｉ）で表わされる炭化水素化合物が好まし
い。However, when these flame retardants are combined with a small amount of flame retardant aid, a remarkable improvement in flame retardancy can be seen. As flame retardant aids used for such purposes, radical generators such as peroxides are generally used, but in the present invention, preferred flame retardant aids to exhibit flame retardancy include 1.
A hydrocarbon compound having a time half-life temperature of 150 to 250''C, particularly a hydrocarbon compound represented by the following formula (I), is preferred.
（Ｒ，’−”Ｒ４は伏素数１以上のアルキル基を示す。(R,'-"R4 represents an alkyl group having a prime number of 1 or more.
）
このような構造を有するものとして、２．３−ジメチル
−２，３−ジフェニルブタン、３．４−ジメチル−５，
４−ジフェニルヘキサン等が４１ｊ’うれる。これらの
難燃助剤の使用量は０２〜２．０重量％であり、２重量
％以上用いても難燃性の更なる向上は期待できず、かつ
コスト的に不利になる。又、かかる難燃助剤を全く用い
ない場合もあり得るが、使用した場合の効果が確認でき
る為には、少なくとも０２重量％以上が必要である。) Those having such a structure include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-5,
4-diphenylhexane etc. are obtained. The amount of these flame retardant aids used is 02 to 2.0% by weight, and even if more than 2% by weight is used, no further improvement in flame retardance can be expected and it is disadvantageous in terms of cost. Although there may be cases where such flame retardant aids are not used at all, in order to confirm the effect when used, at least 0.2% by weight or more is required.
本発明の耐熱性と難燃性を有す２発泡性熱可塑性共重合
体粒子を製造する方法としては、■乳化重合法で上記組
成の共重合体を得た後、ペレット化し、更にオートクレ
ーブ中で易揮発性発泡剤を含浸する方法であシ、難燃剤
及び難燃助剤はベレット化時に練り込まれる。■塊状型
４ 合で上゛記組成の共重合体を得た後、ペレット化し
、更にオートクレーブ中で易揮発性発泡剤を含浸する方
法であシ、難燃剤、難燃助剤は重合時又はベレット化時
に混入せしめられる。■懸濁重合にて上記組成の共重合
体粒子を得、次いで易揮発性発泡剤を含浸する方法であ
り、難燃剤及び難燃助剤は重合時に含有せしめる等の方
法がある。しかしながら、■の乳化重合法に於ては、乳
化重合した後凝固ベレット化を行ない、得られたベレッ
トに発泡剤含浸を行なうという極めて煩雑なプロセスが
必要となり、製造コストが高くなるのみならず、得られ
る樹脂には乳化剤、凝固剤等が多量に混入してしまう為
、発泡性、成形性、強度等の劣ったものしか得られない
という欠点を有する。また■の乳化重合法及び、■の塊
状重合法においては、ベレットの工程が必要であシ、か
つペレット化工程において難燃剤、難燃助剤等が分解を
起こす場合がある。従って、上記■〜■の製造法の中で
は、懸濁重合法が品質的にもプロセス的にも好ましい。The method for producing the heat-resistant and flame-retardant bifoamable thermoplastic copolymer particles of the present invention is as follows: 1. After obtaining a copolymer having the above composition by an emulsion polymerization method, it is pelletized, and then placed in an autoclave. This method involves impregnating a readily volatile foaming agent with a flame retardant and a flame retardant aid during pelletizing. ■Bulk type 4 After obtaining a copolymer with the above composition through polymerization, it is pelletized and further impregnated with an easily volatile blowing agent in an autoclave.The flame retardant and flame retardant aid are added during polymerization or It is mixed in when making pellets. (2) A method in which copolymer particles having the above composition are obtained by suspension polymerization and then impregnated with an easily volatile blowing agent, and flame retardants and flame retardant aids are included during polymerization. However, in the emulsion polymerization method (2), an extremely complicated process of coagulating pellets after emulsion polymerization and impregnating the resulting pellets with a blowing agent is required, which not only increases production costs but also Since the resulting resin contains large amounts of emulsifiers, coagulants, etc., it has the disadvantage that only products with poor foamability, moldability, strength, etc. can be obtained. Furthermore, in the emulsion polymerization method (1) and the bulk polymerization method (2), a pelleting step is required, and flame retardants, flame retardant aids, etc. may decompose in the pelletizing step. Therefore, among the production methods (1) to (2) above, the suspension polymerization method is preferable in terms of quality and process.
しかしながら、従来アルファメチルスチレンを上記の如
く多量使用し、懸濁重合又は塊状重合法で実用に供し得
る程に高分子量の共重合体を得ることは非常に困難とさ
れていた。本発明に於て、この懸濁重合および塊状重合
法によって実用に供し得る程度に高分゛子量のアルファ
メチルスチレン−アクリロニトリル系共重合体の重合を
可能ならしめたものは、特定の開始剤の選択と重合温度
条件の選、択である。重合開始剤として、１０時間半減
期温度が６０〜１２ Ｑ ’（：で、かつｔ−ブトキシ
ラジカルを発生させることの出来る二官能性有機過酸化
物を用い、重合温度８０〜１３５℃で重合する仁とによ
って、初めて上記単量体組成の高分子量共重合体が懸濁
重合法および塊状重合法にて得られるのである。However, it has conventionally been extremely difficult to obtain a copolymer with a high molecular weight that can be used practically by using a large amount of alpha methylstyrene as described above and by suspension polymerization or bulk polymerization. In the present invention, what makes it possible to polymerize an alpha methylstyrene-acrylonitrile copolymer with a high molecular weight to the extent that it can be practically used by the suspension polymerization and bulk polymerization methods is the use of a specific initiator. and selection of polymerization temperature conditions. As a polymerization initiator, a bifunctional organic peroxide with a 10-hour half-life temperature of 60 to 12 For the first time, a high molecular weight copolymer having the above monomer composition can be obtained by suspension polymerization and bulk polymerization.
これらの条件を満たし、実際に使用に供せられる開始剤
としては、ジーｔ−ブチルパーオキシヘキサへイドロテ
レフタレート、１．１−ジ−ｔ−１チルパーオキシ３．
５．５− トリメチルシクロヘキサン、ジ−ｔ−ブチル
パーオキシアゼレート、２，５−ジメチル−２，５−ビ
ス（２−エチルヘキサノニルパーオキシ）ヘキサン、１
．１−ジ−ｔ−ブチルパーオキシシクロヘキサン、１，
３−ビス−（１，−ブチルパーオキシイソプロビル）ベ
ンゼン、２．２−ジー（ｔ−ブチルパーオキシ）ブタン
、４．４−ジーｔ−プチルパーオキシバレリツク酸ｎ−
ブチルエステル、ジ−ｔ−ブチルパーオキシトリメチル
アジベート等があケラバる。Initiators that meet these conditions and are actually used include di-t-butylperoxyhexahedroterephthalate, 1.1-di-t-1-tylperoxy3.
5.5-Trimethylcyclohexane, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-bis(2-ethylhexanonylperoxy)hexane, 1
．． 1-di-t-butylperoxycyclohexane, 1,
3-bis-(1,-butylperoxyisopropyl)benzene, 2,2-di(t-butylperoxy)butane, 4,4-di-t-butylperoxyvaleric acid n-
Butyl esters, di-t-butylperoxytrimethyl adibate, etc. are numerous.
懸濁重合法を採用する場合に用いられる分散剤トシては
、ポリビニルアルコール、ホリヒニルピロリドン、メチ
ルセルロース等の有機分散剤又ハ、第三リン酸カルシウ
ム、ピロリン酸カルシウム、ケイ酸ソーダ、酸化亜鉛、
度酸マグネシウム等の無機分散剤を用いることが出来る
が、無機分散剤を用いる場合には、アルキルベンゼンス
ルフオン酸ソーダ、α−オレフィンスルフオン酸ソーダ
等のアニオン界面活性剤を用いると分散剤の効果は著し
く良好となる。Dispersants used when employing the suspension polymerization method include organic dispersants such as polyvinyl alcohol, pyrrolidone, methylcellulose, tricalcium phosphate, calcium pyrophosphate, sodium silicate, zinc oxide,
An inorganic dispersant such as magnesium chloride can be used, but when an inorganic dispersant is used, an anionic surfactant such as sodium alkylbenzene sulfonate or sodium α-olefin sulfonate may be used to improve the effectiveness of the dispersant. becomes significantly better.
かくして得られる本発明の耐熱性と難燃性を有する発泡
性熱可塑性共重合体粒子は水蒸気、熱風等の加熱媒体に
ょシ所望する倍率まで予備発泡せしめた後、閉塞し得る
が密閉し得ない型中に充填し、水蒸気等の加熱媒体によ
って再び加熱することによって所望の形状を有する耐熱
難燃性発泡成形体となし得る。The thus obtained expandable thermoplastic copolymer particles having heat resistance and flame retardancy of the present invention can be closed but not sealed after being pre-foamed to a desired magnification in a heating medium such as steam or hot air. By filling it into a mold and heating it again with a heating medium such as steam, a heat-resistant and flame-retardant foam molded article having a desired shape can be obtained.
以下本発明を実施例にて説明するが、各実施例において
難燃性の評価については、ＪＩＳ −Ａ−９５１１の方
法による自消時間を測定した結果を示し、耐熱性につい
ては、発泡成形体を１００℃の熱風式均熱乾燥機内忙７
日間放置した後の初期に対する寸法変化率で示した。ま
た成形性については、パールスター９ｏ成形機（東洋機
械金属ＫＫ製）に、縦１１５ｃｍ、横３０ＣＩ１１、厚
さ２ｍｌの成形体を得ることの出来る金型を取付け４０
倍の発泡体を成形した時の、得られる成形体の外観によ
って評価した。The present invention will be explained below with reference to examples. In each example, the evaluation of flame retardancy is based on the results of measuring the self-extinguishing time according to the method of JIS-A-9511, and the heat resistance is 7 in a hot air soaking dryer at 100℃
It is expressed as a dimensional change rate with respect to the initial value after being left for days. Regarding moldability, a mold capable of obtaining a molded product with a length of 115 cm, a width of 30 CI11, and a thickness of 2 ml was installed on a Pearl Star 9o molding machine (manufactured by Toyo Kikinzoku KK).
Evaluation was made based on the appearance of the resulting molded product when a foam of twice the size was molded.
実施例１
攪拌機付きオートクレーブ中に純水１００重量部、第三
リン酸カルシウム０２重量部、ドデシルベンゼンスルホ
ン酸ソー７ａ、ｏｏｓＭＩｋｍヲ仕込゛んだ後、攪拌下
、アルファメチルメチレフ３０重ｆｉ部、アクリロニト
リル２０重１［、スチレン５０重量部からなる単量体に
ヘキサブロムシクロドデカン４０重量部、２．５−ジメ
チル−２，３−ジフェニルブタン０．５ ｌｉ ｉ 部
（！： ）ルエン０．５重量部、１．１−ジ−ｔ−ブチ
ルパーオキシ−５，３，５−トリメチルシクロヘキサン
０３重量部を混合してオートクレーブ中に加え、１００
℃で８時間の重合を行なった。得られた組成物の重合転
化率は９９４％であった。次いで、ブタン１０重量部を
加え、１００℃で８時間の発泡剤含浸を行なった。得ら
れた発泡性熱可塑性共重合体を樹脂（Ａ）とした。樹脂
（Ａ）を水蒸気で加熱することによシ、見掛倍率４０倍
に予備発泡した後、閉塞し得るが密閉し得ない金型に充
填し水蒸気で加熱することによシ４５ｎＸ３０ｍ×２ｃ
ＩＲの板状発泡成形体を得た。Example 1 After charging 100 parts by weight of pure water, 02 parts by weight of tribasic calcium phosphate, 7a of dodecylbenzenesulfonic acid, and oosMIkm into an autoclave equipped with a stirrer, 30 parts by weight of alpha methyl methyl ref and 20 parts by weight of acrylonitrile were added under stirring. A monomer consisting of 50 parts by weight of styrene, 40 parts by weight of hexabromocyclododecane, 0.5 parts by weight of 2,5-dimethyl-2,3-diphenylbutane (!: ) 0.5 parts by weight of toluene , 0.3 parts by weight of 1.1-di-t-butylperoxy-5,3,5-trimethylcyclohexane were mixed and added to an autoclave, and 100
Polymerization was carried out at ℃ for 8 hours. The polymerization conversion rate of the obtained composition was 994%. Next, 10 parts by weight of butane was added, and impregnation with a blowing agent was carried out at 100° C. for 8 hours. The obtained expandable thermoplastic copolymer was designated as resin (A). By heating the resin (A) with steam, the resin (A) is pre-foamed to an apparent magnification of 40 times, and then filled into a mold that can be closed but cannot be sealed, and heated with steam.
An IR plate-shaped foam molded product was obtained.
該板状発泡成形体を１００℃の熱風式均熱乾燥機内に１
週間放置した後の、初期寸法に対する寸法変化率を調べ
た。また該板状発泡成形体の表皮を熱線にて切り取り、
２．５ （２Ｘ １（１）Ｘ２０備の試験片を作成し、
ＪＩＳ−Ａ−９５１１に基づいて成形体の自己消火時間
を調べ、結果を表−１に示した。The plate-shaped foam molded product was placed in a hot air soaking dryer at 100°C.
After being left for a week, the dimensional change rate with respect to the initial dimension was investigated. In addition, the skin of the plate-shaped foam molded product is cut with a hot wire,
2.5 (Create a test piece of 2 x 1 (1) x 20 pieces,
The self-extinguishing time of the molded body was investigated based on JIS-A-9511, and the results are shown in Table 1.
実施例２〜４
実施例１において、ヘキサブロムシクロトチカンの代り
に表−１に示す難燃剤を用いた以りは実施例１と同様に
して実験−を行なった結果壱表−１に示した。Examples 2 to 4 Experiments were conducted in the same manner as in Example 1, except that the flame retardants shown in Table 1 were used instead of hexabromcyclototicane. The results are shown in Table 1. Ta.
比較例１〜５
実施例１において、ヘキサブロムシクロトチカン及び２
．３−ジメチル−２，３−ジフェニルブタンを用いなか
った場合、又はヘキサブロムシクロと、、デカンの代り
に表−１に示す難燃剤を月いた以外実施例１と同様にし
て実験を行なつに結果を表−１に示す。Comparative Examples 1 to 5 In Example 1, hexabromcyclototican and 2
．． The experiment was carried out in the same manner as in Example 1, except that 3-dimethyl-2,3-diphenylbutane was not used, or hexabromocyclo was used, and the flame retardant shown in Table 1 was used instead of decane. The results are shown in Table-1.
比較例４
実施例１において、ヘキサブロムシクロトチカンの量を
８０重量部とし、２．３−ジメチル−２，６−ジフェニ
ルブタンを用いない以外は実施例１と同様にして実験を
打力った結果を表−２に示した。Comparative Example 4 The experiment was carried out in the same manner as in Example 1 except that the amount of hexabromcyclototicane was 80 parts by weight and 2,3-dimethyl-2,6-diphenylbutane was not used. The results are shown in Table 2.
１、Ｉｌ燃剤量は４０部、ただし比較例１はなし。1. The amount of Il fuel was 40 parts, except in Comparative Example 1.
２、蕪燃助剤として、２，３−ジメチル−２，３−ジフ
ェニルブタンを０．５部用いた。ただし、比較例１はな
し。2. 0.5 part of 2,3-dimethyl-2,3-diphenylbutane was used as a turnip combustion aid. However, there was no Comparative Example 1.
※成形性 ◎：非常に良好、 ○：良好×：不良*Moldability ◎: Very good, ○: Good ×: Poor
Claims (7)
メチレフ１０〜８０重ｉ％、アクリロニトリル５〜５０
重量％、更にスチレン、クロルスチレン、バラメチフレ
スチレン、ｔ−ブチルスチレン、アクリル酸エステル、
メタクリル酸エステルから選ばれた少なくとも１種の化
合物０〜７０重量％であり、易揮発性発泡剤２〜１５重
量％及び分解温度が１８０〜２５０″Ｃの難燃剤１〜１
５重量％と、１時間半減期温度が１５０〜２５ Ｑ １
：の難燃助剤０．２〜２．０重量％を含有してなる発泡
性熱可塑性共重合体粒子。(1) The monomer composition constituting the polymer is 10 to 80% by weight of alpha methyl methyleph, 5 to 50% by weight of acrylonitrile.
% by weight, further styrene, chlorstyrene, rosemethylene styrene, t-butylstyrene, acrylic ester,
0 to 70% by weight of at least one compound selected from methacrylic acid esters, 2 to 15% by weight of an easily volatile blowing agent, and a flame retardant 1 to 1 with a decomposition temperature of 180 to 250''C.
5% by weight and the 1 hour half-life temperature is 150~25 Q 1
Expandable thermoplastic copolymer particles containing 0.2 to 2.0% by weight of a flame retardant aid.
許請求の範囲第１項記載の発泡性熱可塑性共重合体粒子
。(2) The expandable thermoplastic copolymer particles according to claim 1, wherein the flame retardant has a melting point of 80° C. or higher.
第１項又は第２項記載の発泡性熱可塑性共重合体粒子。(3) The expandable thermoplastic copolymer particles according to claim 1 or 2, wherein the flame retardant is a halogen flame retardant.
許請求の範囲第１項記載の発泡性熱可塑性共重合体粒子
。(4) The expandable thermoplastic copolymer particles according to claim 1, wherein the flame retardant is hexabromcyclododecane.
合物である特許請求の範囲第１項記載の発泡性熱可塑性
共重合体粒子。 （Ｒ，”Ｒ，は度素数１以上のアルキル基を示す。）(5) The expandable thermoplastic copolymer particles according to claim 1, wherein the flame retardant auxiliary agent is a hydrocarbon compound represented by the following formula (I). (R, "R" represents an alkyl group with a degree prime number of 1 or more.)
ルブタンおよび／又は５．４−ジメチル−３，４−ジフ
ェニルヘキサンである特許請求の範囲第５項記載の発泡
性熱可塑性共重合体粒子。(6) The foamable thermoplastic according to claim 5, wherein the flame retardant aid is 2,3-dimethyl-2,3-diphenylbutane and/or 5,4-dimethyl-3,4-diphenylhexane. Copolymer particles.
許請求の範囲第１項記載の発泡性熱可塑性共重合体粒子
。(7) The expandable thermoplastic copolymer particles according to claim 1, wherein the content of the 1ift fuel agent is 3 to 10% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6462884A JPS60206845A (en) | 1984-03-30 | 1984-03-30 | Expandable thermoplastic copolymer particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6462884A JPS60206845A (en) | 1984-03-30 | 1984-03-30 | Expandable thermoplastic copolymer particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60206845A true JPS60206845A (en) | 1985-10-18 |
| JPH0461896B2 JPH0461896B2 (en) | 1992-10-02 |
Family
ID=13263708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6462884A Granted JPS60206845A (en) | 1984-03-30 | 1984-03-30 | Expandable thermoplastic copolymer particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60206845A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0436383A2 (en) * | 1989-12-29 | 1991-07-10 | ARCO Chemical Technology, L.P. | Process for the preparation of expandable vinyl aromatic polymer particles containing hexabromocyclododecane |
| JPH04154847A (en) * | 1990-10-19 | 1992-05-27 | Sekisui Plastics Co Ltd | Flame retardant expandable resin particle |
| EP0680831A1 (en) * | 1994-05-04 | 1995-11-08 | Dsm N.V. | Shaped article with a marking on a thermoplastic substrate and a process for the manufacture of the shaped article |
| JP2016164213A (en) * | 2015-03-06 | 2016-09-08 | 株式会社カネカ | Foamable resin particle and manufacturing method therefor |
| JP2019521196A (en) * | 2016-07-08 | 2019-07-25 | ベルサリス、ソシエタ、ペル、アチオニＶｅｒｓａｌｉｓ Ｓ．Ｐ．Ａ． | Foamable composition containing an aromatic vinyl polymer having self-digestion and improved processability |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52142764A (en) * | 1976-05-24 | 1977-11-28 | Arco Polymers Inc | Antioxidant for |
| JPS532910A (en) * | 1976-06-30 | 1978-01-12 | Matsushita Electric Works Ltd | Fitting method of ceiling board |
| JPS543510A (en) * | 1977-06-09 | 1979-01-11 | Teac Corp | Cassette tape magnetic recorder*reproducer |
| JPS5765735A (en) * | 1980-09-13 | 1982-04-21 | Kanegafuchi Chem Ind Co Ltd | Heat-resistant expandable synthetic resin particle and molded article thereof |
| JPS57111332A (en) * | 1980-12-27 | 1982-07-10 | Badische Yuka Co Ltd | Self-extinguishing polystyrene resin particle |
| JPS57111337A (en) * | 1980-12-29 | 1982-07-10 | Achilles Corp | Foamable polystyrene resin composition with flame retardancy |
| JPS57185328A (en) * | 1982-04-07 | 1982-11-15 | Dow Chemical Co | Foam-linked body with foamable synthetic resin particles |
-
1984
- 1984-03-30 JP JP6462884A patent/JPS60206845A/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52142764A (en) * | 1976-05-24 | 1977-11-28 | Arco Polymers Inc | Antioxidant for |
| JPS532910A (en) * | 1976-06-30 | 1978-01-12 | Matsushita Electric Works Ltd | Fitting method of ceiling board |
| JPS543510A (en) * | 1977-06-09 | 1979-01-11 | Teac Corp | Cassette tape magnetic recorder*reproducer |
| JPS5765735A (en) * | 1980-09-13 | 1982-04-21 | Kanegafuchi Chem Ind Co Ltd | Heat-resistant expandable synthetic resin particle and molded article thereof |
| JPS57111332A (en) * | 1980-12-27 | 1982-07-10 | Badische Yuka Co Ltd | Self-extinguishing polystyrene resin particle |
| JPS57111337A (en) * | 1980-12-29 | 1982-07-10 | Achilles Corp | Foamable polystyrene resin composition with flame retardancy |
| JPS57185328A (en) * | 1982-04-07 | 1982-11-15 | Dow Chemical Co | Foam-linked body with foamable synthetic resin particles |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0436383A2 (en) * | 1989-12-29 | 1991-07-10 | ARCO Chemical Technology, L.P. | Process for the preparation of expandable vinyl aromatic polymer particles containing hexabromocyclododecane |
| JPH04154847A (en) * | 1990-10-19 | 1992-05-27 | Sekisui Plastics Co Ltd | Flame retardant expandable resin particle |
| EP0680831A1 (en) * | 1994-05-04 | 1995-11-08 | Dsm N.V. | Shaped article with a marking on a thermoplastic substrate and a process for the manufacture of the shaped article |
| BE1008341A3 (en) * | 1994-05-04 | 1996-04-02 | Dsm Nv | Form part of a mark in surface of a thermoplastic plastic and method for form part of preparation. |
| JP2016164213A (en) * | 2015-03-06 | 2016-09-08 | 株式会社カネカ | Foamable resin particle and manufacturing method therefor |
| JP2019521196A (en) * | 2016-07-08 | 2019-07-25 | ベルサリス、ソシエタ、ペル、アチオニＶｅｒｓａｌｉｓ Ｓ．Ｐ．Ａ． | Foamable composition containing an aromatic vinyl polymer having self-digestion and improved processability |
| US11359066B2 (en) | 2016-07-08 | 2022-06-14 | Versalis S.P.A. | Expandable compositions containing aromatic vinyl polymers having self-extinguishing properties and improved processability |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0461896B2 (en) | 1992-10-02 |
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