200934814 六、發明說明： 【發明所屬之技術領域】 本發明係關於—種難燃性發泡 \ 其製造方法。更詳而言之 ^乙埽類樹脂粒子月 辛烧作為難燃劑之難_發泡性=關於-種使用四_ 造方法。 烯類樹脂粒子及其製 【先前技術】 ❹ ❹ 自以在，本乙缔類播.、 度及隔熱性，故常使用於心材體係因具有優異之強 發泡成形體係使笨乙缔類單^懸浮=此之笨乙婦類樹脂 脂粒子，於所得到之笨乙歸類樹脂教=得到苯乙嫦類樹 得到發泡性苯乙烯類樹脂粒子， 3浸物理發泡劑而 類樹脂粒子預備發泡，藉以得，所得到之發泡性苯乙烯 子，並使所得到之預備發泡=二歸類樹赌預備發泡粒 内雨發泡，在預備發泡粒子間經由於所希望形狀的模具 著一體化而製造。 、~等之發泡壓使之熱融 另外，上述本乙烯類樹脂 題點。尤其，使用於建筚材 / >體係具有易燃之問 之原因。因此，係心當火災之際亦成為延燒 燃劑而謀求此問題之解決。樹脂發泡成形體中添加難 難=之添加方法已知有：溶解 法，或與物理發泡劑同砗各岬頰早骽之万 法。改於苯乙稀類樹脂粒子中之方 r袁二齡";5气记載於日本特開_-335891號公報 〈專利文獻υ及日本特開扇2、19侧號公報（專利文獻2) 320897 3 200934814 之方法，後者之方法包括記載於日本特公平6-18918說公 報（專利文獻3)及日本特開2〇〇7_2466〇6號公報（專剎文獻 4)之方法。 [專利文獻1]日本特開2003-335891號公報 [專利文獻2]日本特開2002_194130號公報 [專利文獻3]日本特公平6_18918號公報 [專利文獻4]日本特開2007-246606號公報 【發明内容】 (發明欲解決之課題） © 在前者之方法中，主要使用六溴環十二烷（HBCp)作為 難燃劑。HBCD係被擔心蓄積於活體内之物質，期望滅少其 使用。在後者之方法中係因於苯乙烯類樹脂粒子中含浸難 燃劑，故其含浸量有限’以含浸更多之難燃劑，期爹提昇 難燃性。 又，若於苯乙烯類樹脂粒子中大量含有難燃劑，難燦 劑作為造核劑功能’所得到之苯乙烯類樹脂發泡體即有氣 泡技會太細之問題。此課題係於上述後者之方法中造成特 〇 別不良影響。亦即’在後者之方法中’苯乙烯類樹脂粒子 之表面附近存在許多之難燃劑’故於預備發泡粒子内所形 成之氣泡只有表層部分變細。其結果，無法承受氣泡因成 形而得到發泡成形體時之熱’而產生熔解，對發泡成型品 之外觀造成不良影響。又，於苯乙烯類樹脂粒子之表面附 近存在許多難燃劑’故藉難燃劑而於預備發泡時預備發泡 粒子間相互融著結合’易產生所謂黏結之傾向。進一步， 320897 4 200934814 難燃劑於發泡劑含浸用之液中引起2次凝集，俾使難燃劑 之分散不均。其結果’苯乙烯類樹脂粒子對難燃劑之吸收 不均。而吸收不均，使得一部分存在許多吸收難燃劑之粒 子，其粒子之耐熱性變差。因此，無法充分承受發泡成形 品之成形時的加熱’因此收縮而有成為硬化粗的情形。發 泡成形品係藉一般錄絡合金（Nichrome)切割線成形為特定 的形狀，但其時於硬化粒上會使鎳鉻合金切割線跳開，而 於鎳鉻合金切割線面上產生凹凸狀之條紋，恐明顯降低製 品之價值。又，凹凸狀之條紋，在使發泡成形品與面板貼 合之用途中’恐無法得到充分的接著強度。 進一步’亦有苯乙烯類樹脂預備發泡粒子間的熱融著 性會降低之問題。 (用以解決課題之手段） 本發明之發明人等發現可提供一種發泡性苯乙婦類樹 脂粒子，其係使用特定量之特定難賴，在將物理發 ❹ 之含浸溫度設為敎溫度下，俾可得到發泡之際粒子間的 =性優異同時具有優異之難燃性的發泡成形品，終完 成本發明。 合而得到苯乙歸類樹脂粒子時，相對於前述 ⑽重量份’添加四漠環枝0.45至2〇重H早 於前述苯乙烯類單體的懸浮聚合中 〇量伤，…、、邊 浸溫度調整至80至i1〇t，—邊物$後―邊使 4㈣理發，含浸於前 320897 5 200934814 苯乙烯類樹脂粒子，俾得到難燃性發泡性苯乙烯類樹脂粒 子。 進一步，若依本發明，可提供一種難燃性發泡性笨乙 烯類樹脂粒子，其係具備笨乙烯類樹脂粒子、前述苯乙烯 類樹脂粒子中所含有的物理發泡劑及四溴環辛烷； 前述四溴環辛烷為若於前述苯乙烯類樹脂粒子之表層 部所含有的四溴環辛烷含有率為a(重量％)，於前述苯乙烯 類樹脂粒子之全體所含有的四溴環辛烷含有率為b(重量 %)，以滿足式aSl. lxb之關係的方式，包含於前述苯乙烯 〇 類樹脂粒子； 於前述苯乙稀類樹脂粒子之全體所含有的四溴環辛烷 含有率相對於苯乙烯類樹脂粒子1〇〇重量份，為0.45至 2. 0重量份； 發泡成發泡倍數50倍時，可賦予50至350 //m之平均 氣泡徑的發泡體。 (發明之效果） q 若依本發明之製造方法，可提供一種難燃性發泡性苯 乙烯類樹脂粒子，其係可控制氣泡徑，發泡時無氣泡粗密 之情形，且成型時之熱融著性良好者。 又，於懸浮聚合時使用界面活性劑，可提昇懸浮聚合 類之單體混合物的液滴之分散安定性。 於單體混合物中含有難燃助劑，可提昇發泡性苯乙烯 類樹脂粒子之難燃性。 以使前述難燃性發泡性苯乙烯類樹脂粒子發泡成50 6 320897 200934814 倍所得到之發泡成形體具有50至350 /zm之平均氣泡徑的 方式，調整含浸溫度，俾可提供熱融著性更良好之發泡性 苯乙烯類樹脂粒子。 【實施方式】 (用以實施發明之最佳形態） 在本發明中首先使苯乙烯類單體懸浮聚合而得到苯乙 烯類樹脂粒子時，相對於苯乙烯類單體而添加四溴環辛烷 (TBC0)與聚合起始劑。 ® 苯乙烯類單體係可舉例如苯乙烯、α-曱基苯乙烯、對 甲基苯乙烯、第三丁基苯乙烯、氯化苯乙烯等。此等之單 體可單獨或混合2種以上而使用。其中尤宜為苯乙烯。又， 亦可與甲基丙烯酸酯、丁基丙烯酸酯、甲基丙烯酸甲酯、 甲基丙烯酸乙酯、曱基丙烯酸鯨蠟酯等之丙烯酸及曱基丙 烯酸之酯、或丙烯腈、二甲基富馬酸酯、乙基富馬酸酯等 之單體與苯乙烯類單體共聚合。進一步，亦可使二乙烯基 q 苯、烷撐二醇二甲基丙烯酸酯等之2官能性單體與苯乙烯 類單體共聚合。 TBCO係相對於苯乙烯類單體100重量份，可在0.45 至2. 00重量份的範圍使用。在此範圍内係可確保難燃性及 成型時之熱融著性，可抑制氣泡粗密。 聚合起始劑無特別限定而可適當選擇適於聚合溫度之 聚合起始劑。可舉例如過氧化苯曱醯、過氧化月桂醯、過 氧化苯甲酸第三丁酯、過氧化三曱基乙酸第三丁基酯、過 氧化異丙基碳酸第三丁酯、過氧化乙酸第三丁酯、2, 2-二 7 320897 200934814 (第三丁基過氧化）丁烷、第三丁基過氧化-3, 3, 5-三曱基環 己酸酯、二第三丁基過氧化六氫對酞酸酯、1,1-二第三丁 基過氧化-3, 3, 5-三曱基環己烷等之有機過氧化物、或偶氮 雙異丁腈、偶氮雙二曱基戊腈等之偶氮化合物。此等之聚 合起始劑可單獨或混合2種以上而使用。聚合起始劑係相 對於苯乙烯類單體100重量份，可在0.05至3.0重量份的 範圍使用。 使TBCO溶解於苯乙烯類單體以得到單體混合物。單體 混合物亦可含有難燃助劑。難燃助劑係可舉例如枯基過氧 〇 化氫、過氧化二枯基、第三丁基過氧化氫、2, 3-二甲基-2, 3-二苯基丁烷等。難燃助劑係相對於苯乙烯類單體100重量 份，可使用0. 1至0. 5重量份。 單體混合物係於水性介質中分散而供給至懸浮聚合。 水性介質係可舉例如水、或水與水溶性有機介質（例如 曱醇、乙醇）之混合物。水性介質亦可含有界面活性劑、分 散劑等之添加劑。 0 界面活性劑可舉例如陰離子性界面活性劑、陽離子性 界面活性劑、兩性離子性界面活性劑、非離子性界面活性 劑。 陰離子性界面活性劑係可舉例如油酸鈉、蓖麻油鉀等 之脂肪酸油、月桂基硫酸鈉、月桂基硫酸銨等之烷基硫酸 酯鹽、十二烷基苯磺酸鈉等之烷基苯磺酸鹽、烷基萘磺酸 鹽、烷磺酸鹽、二烷基磺基琥珀酸鹽、烷基磷酸酯鹽、萘 確酸福馬林縮合物、聚氧乙烯院基苯基趟硫酸S旨鹽、聚氧 8 320897 200934814 乙烯烷基硫酸酯鹽等。 非離子性界面活性劑可舉例如聚氧乙烯烷基醚、聚氧 乙烯烷基苯基醚、聚氧乙烯脂肪酸酯、山梨糖醇酐脂肪酸 酯、聚氧山梨糖醇酐脂肪酸酯、聚氧乙烯烷基胺、甘油脂 肪酸酯、氧乙烯-氧丙烯嵌段聚合物等。 陽離子性界面活性劑係可舉例如月桂基胺乙酸鹽、硬 脂基胺乙酸鹽等之烷基胺鹽、氯化月桂基三甲基銨等之四 級銨鹽等。 ® 兩性離子性界面活性劑可舉例如氧化月桂基二甲基 胺、或磷酸酯系或亞磷酸酯系界面活性劑。 上述界面活性劑可單獨或組合2種以上而使用。界面 活性劑係相對於水性介質100重量份，可在0.002至1.0 重量份的範圍使用。 分散劑可舉例如聚乙烯醇、曱基纖維素、聚乙烯吼咯 烷酮、聚丙烯醯胺等之水溶性高分子、焦磷酸鎂、磷酸三 Q 妈、經基雄灰石等之難溶性無機鹽等。 此等之分散劑可單獨或混合2種以上而使用。分散劑 係相對於苯乙烯類單體100重量份，可在0. 2至10重量份 之範圍使用。 苯乙烯類單體係供給於懸浮聚合。懸浮聚合一般係在 50至120°C下進行1至20小時。懸浮聚合之結果，可得到 苯乙烯類樹脂粒子。 進一步，於懸浮聚合中或懸浮聚合後經由使物理發泡 劑含浸於苯乙烯類樹脂粒子，可得到難燃性發泡性苯乙烯 9 320897 200934814 類樹脂粒子。此處，含浸時之含浸溫度可調整於肋至 °C。經由調整而可提供一種難燃性發泡性笨乙埽類樹月^ 子，其係可控制氣泡徑，發泡時無氣泡粗密之情形e 時之熱融著性良好者。 成型 ，於懸浮聚合中’物理發_於苯乙烯類樹脂粒子 含浸，可將物理發泡劑壓入於水性介質來進行。又，殮… 聚合後使物理發泡劑含浸於笨乙稀類樹脂粒子時，可= 二:質取出苯乙烯類樹脂粒子而含浸，亦可含浸於水性： 〇 物理發泡劑係指不經分解而直接具有發泡功能 劑’相當於所謂的揮發性發泡劑。物理發泡劑可舉例如丙 烷、正丁燒、異丁院、正戊院、異戊烧、己院等之脂肪族 烴類。此等物理發泡劑可單獨或併用2種以上。 、 所得敎難祕们紐苯__絲 可例如為0.3至2. 0咖。 〇粒^ 〇 、難燃性發泡性笨乙烯類樹脂粒子係經過公知之預 泡步驟及發泡成形步驟，而成為發泡成形體。尤龙 成倍時，可使構成發泡成形體之氣泡的平均氣泡後為 50至35G_的範圍。料此範圍，構成發泡成形體 泡粒子的熱融著性為良好。 發 :包性= 中亦可提供一種由上述方法而得到之難燃性發 …本乙_樹脂粒子。難燃性發泡 =子子之表層部所含有的四漠環梅有=: )於粒子之全體所含有的四漠環辛院含有率為b(重量 320897 10 200934814 %以滿足式1. lxb之關係的方式，含有四漠環辛炫。 以滿足此關係’可提供—種同時滿足難燃性與熱融著性之 .兩者的難燃性發泡性苯乙烯麵絲子。更佳係以式“ 1. 05xb所示的關係。 此處’由於粒子之表層部所含有的四溴環辛烷含有率 a ’很難直接測定’故係依以下之方法所測定之值。亦即， 從使難燃性發泡性苯乙烯類樹脂粒子發泡成50倍之發泡 Q 成形體之表面切出厚0.2mm之試驗片。發泡成形體之表面 係由難燃性發泡性苯乙烯類樹脂粒子之表面層所構成，故 此試驗片係表示難燃性發泡性苯乙烯類樹脂粒子的表面層 之狀態。測定試驗片中之四溴環辛烷量，算出相對於試驗 片總重量之比，得到粒子表層部中所含有的四溴環辛烷含 有率a(重量％)。又，測定法之細節係記載於實施例中。 另外，於粒子之全體所含有的四溴環辛烷含有率b意 指作為難燃性發泡性苯乙稀類樹脂粒子製造時之原料的四 ©溴環辛烷量對苯乙烯類單禮之比。 [實施例] 卩下，依據實施例而0艘地說明本發明，但本發明 係不受此等實施例限定。又，苯乙烯類樹脂粒子之分子量、 體積發泡倍率、發泡伴數、難燃性、平均氣泡徑及熱融著 性之測定法記载於下述。 (本乙烯類樹脂粒子之八孑責） 使用凝膝渗透J分析(趴)，測定重量平均分子量 (黯）。其測定方法係如%述。又，重量平均分子量㈤意 320897 200934814 指聚笨乙烯（ps)換算重量平均分子量。 使試料50mg溶解於四氫呋喃（THF)IO毫升，以非水系 0. 45 之層析盤過濾後，使用色層分析而測定。色層分 析之條件係如下述。 液體色層分析：Tosoh公司製、商品名「凝膠滲透色 層分析HLC-8020」 管柱：Tosoh公司製、商品名「TSKgel GMH-XL-L」0 7.8mmx30cmx2 支 管柱溫度：40°C 載氣：四氫呋喃（THF) 載氣流量：1毫升/分鐘 注入幫浦溫度：35°C 檢測：RI 注入量：1〇〇微升 檢量線用標準聚苯乙烯：昭和電工公司製、商品名 「shodex」重量平均分子量：103000〇與T〇s〇h公司製： 重量平均分子量：5480000、3840000、355000、102〇〇〇、 37900 、 9100 、 2630 、 870 (體積發泡倍數） 體積發泡倍數係使預備發泡粒子作為試料而於量筒 内自然落下之後，敲打量筒底部而使試料容積為一定| 量並依下式求算。如為笨乙埽類樹 體積發泡倍數（倍）=量筒中之試料容積（mi)/試料質 320897 12 200934814 量（g)x樹脂比重 (發泡倍數） 發泡倍數係以有效數字成為3次方以上之方式測定發 泡成形體的試驗片（例50x50x25mm)的尺寸與質量，依下气 求算出。如為苯乙烯類樹脂時樹脂比重為1. 0。 發泡倍數（倍）=試驗片體積（cm3)/試驗試質量（§)><樹 脂比重 (難燃性） Ο 試驗片係從發泡成形體切取厚l〇mm、長200mm、寬25min 5片’於試驗片賦予規定之著火界限指示線及燃燒界限指 示線。使試驗片以火源用蠟蝎燃燒至著火界限指示線之 後’離開火焰，測定從其瞬間至火焰消滅為止之時間（秒）。 火焰消滅為止之時間（秒）以試驗數5之平均不超過3秒， 全無超過燃燒界限指示線而燃燒者即為及格。火源用纖虫萄 係使用疋常燃燒％· ’芯之長度約1 〇mm之時，火焰之長度 ❹ 50mm以上、粗度約7mm以上者。 (平均氣泡徑） 切割發泡成形體，從切割面之裁切面外侧使1/1()至 9/10以上内側以掃描型電子顯微鏡（日立製作所公司製 S-3000N)擴大成1〇〇倍而進行攝影。將所攝影之影像各4 影像印刷於A4用紙上，從在任意之一直線上（長度6〇mm) 之氣泡數依下述式算出氣泡的平均弦長（t)。但’任意的直 線儘可能地避免乳泡以接點接觸於所畫之直線（接觸時即 計算該接觸之氣泡數在）。計測係6處。 13 320897 200934814 平均弦長t=60/(氣泡數χ照片的倍率） 繼而，依下式算出氣泡徑D。 D=t/0.616 (熱融著性） 成形後，使發泡成形體以70t乾燥48小時後，使用 鎳鉻合金切片機於厚度方向之中心附近切取厚約5〇mm 者’所切取之350x450x50mm的板狀成形品於長度方向的中 央部剖半。求算出存在於剖面之全粒子中，發泡粒子本身 經裁斷之粒子對全粒子的比率（％)。8〇%以上之融著比率為 ◎，60 1未滿概之融著比率為〇，4〇至未滿6〇%之融著 比率為△’未滿40%之融著比率為χ。 實施例1 於100升之高壓銷中，200934814 VI. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a flame retardant foaming method. More specifically, it is difficult to use acetaminophen particles as a flame retardant. _ Foaming property = About the use of four kinds of methods. Ethylene resin particles and their preparation [Prior Art] ❹ ❹ Self-contained, this kind of B-type broadcast, degree and heat insulation, so it is often used in heartwood systems because of its excellent strong foam forming system ^ Suspension = This kind of stupid women's resin grease particles, in the obtained stupid B classified resin teach = get styrene tree to obtain foaming styrene resin particles, 3 dip physical foaming agent and resin particles Pre-foaming, by which the obtained foaming styrene is obtained, and the obtained preliminary foaming = two-category tree gambling is prepared for foaming in the foaming granules, and is desired between the preliminary foaming particles. The shape of the mold is integrated and manufactured. The foaming pressure of ~, etc. makes it hot and melt. In addition, the above-mentioned vinyl resin is the subject. In particular, the use of the Coffin / > system is the cause of flammability. Therefore, when the heart is in the fire, it becomes a burning agent and seeks to solve this problem. A method of adding difficulty in the addition of the resin foam molded body is known as a dissolution method or a method in which the physical foaming agent is used in the same manner as the physical foaming agent. In the case of the styrene-based resin particles, it is described in Japanese Laid-Open Patent Publication No. _-335891 (Patent Document No. 2, Japanese Patent Laid-Open No. 2, No. 19 (Patent Document 2) 320897 In the method of the method of the invention, the method of the latter is described in Japanese Patent Publication No. 6-18918 (Patent Document 3) and Japanese Patent Application Laid-Open No. Hei. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Contents] (The problem to be solved by the invention) © In the former method, HBCD is mainly used as a flame retardant. HBCD is worried about the accumulation of substances in the living body, and it is expected to reduce its use. In the latter method, since the styrene resin particles are impregnated with the flame retardant, the impregnation amount is limited to impregnate more flame retardant, and the flame retardancy is improved. Further, when the styrene resin particles contain a large amount of a flame retardant, the styrene resin foam obtained as a nucleating agent function is a problem that the bubble technique is too fine. This subject is particularly devastating in the latter method. That is, in the latter method, a large number of flame retardants are present in the vicinity of the surface of the styrene resin particles. Therefore, only the surface layer portion of the bubbles formed in the preliminary expanded particles is tapered. As a result, it is impossible to withstand the heat generated when the bubble is obtained by the formation of the foamed molded body, and the melt is formed, which adversely affects the appearance of the foamed molded article. Further, there are many flame retardants in the vicinity of the surface of the styrene resin particles. Therefore, the foaming particles are preliminarily bonded to each other at the time of preliminary foaming by the flame retardant, and tend to cause so-called sticking. Further, 320897 4 200934814 The flame retardant causes two agglomerations in the liquid for impregnation of the foaming agent, and causes uneven dispersion of the flame retardant. As a result, the absorption of the flame retardant by the styrene resin particles was uneven. However, uneven absorption causes a part of the particles to absorb the flame retardant, and the heat resistance of the particles is deteriorated. Therefore, it is not possible to sufficiently withstand the heating at the time of molding of the foamed molded article, and thus shrinks and becomes hardened. The foamed molded product is formed into a specific shape by a Nichrome cutting line, but at the same time, the nickel-chromium alloy cutting line is jumped on the hardened grain, and the unevenness is formed on the nickel-chromium alloy cutting line surface. The stripes may obviously reduce the value of the product. Further, in the use of the uneven streaks in the use of bonding the foamed molded article to the panel, it is feared that sufficient adhesion strength cannot be obtained. Further, there is a problem that the heat fusion property between the styrene resin-prepared foam particles is lowered. (Means for Solving the Problem) The inventors of the present invention have found that it is possible to provide a foamable styrene-based resin particle which is specific to the use of a specific amount, and the impregnation temperature of the physical hair is set to the temperature of 敎In the meantime, the foamed molded article having excellent incompatibility between particles and having excellent flame retardancy at the time of foaming can be obtained, and the present invention has been completed. When the styrene-based resin particles are obtained in combination, the 0.45 to 2 〇 weight H is added to the (10) parts by weight of the above-mentioned (4) parts by weight, and the amount of strontium in the suspension polymerization of the styrene monomer is earlier than that of the above-mentioned styrene monomer. The temperature is adjusted to 80 to i1〇t, and the side material is $ after the side is made 4 (four) haircut, impregnated with the front 320897 5 200934814 styrene resin particles, and the flammable expandable styrene resin particles are obtained. Further, according to the present invention, it is possible to provide a flame-retardant foamable styrene-based resin particle having a stupid ethylene resin particle, a physical foaming agent contained in the styrene resin particle, and tetrabromocyclooctyl The tetrabromocyclooctane is a tetrabromocyclooctane content in the surface layer portion of the styrene resin particles, and the content of the tetrabromocyclooctane is a (% by weight), and is contained in the entire styrene resin particles. The bromocyclooctane content is b (% by weight), and is included in the styrene oxime resin particle in a manner to satisfy the relationship of the formula aS1.lxb; and the tetrabromo ring contained in the entire styrene resin particle The octane content is 0.45 to 2.0 parts by weight based on 1 part by weight of the styrene resin particles; and when the foaming ratio is 50 times, the average bubble diameter of 50 to 350 //m can be imparted. Bubble body. (Effect of the Invention) q According to the production method of the present invention, it is possible to provide a flame-retardant expandable styrene-based resin particle which can control the bubble diameter, has no bubble coarseness during foaming, and is hot during molding. Those who are well-melted. Further, by using a surfactant in the suspension polymerization, the dispersion stability of the droplets of the monomer mixture of the suspension polymerization can be improved. The inclusion of a flame retardant in the monomer mixture improves the flame retardancy of the expandable styrene resin particles. The foamed molded body obtained by foaming the flame-retardant expandable styrene-based resin particles into 50 6 320 897 200934814 times has an average bubble diameter of 50 to 350 /zm, and the impregnation temperature is adjusted to provide heat. Expandable styrene resin particles having better fusion properties. [Embodiment] (Best Mode for Carrying Out the Invention) In the present invention, when a styrene monomer is first suspended and polymerized to obtain a styrene resin particle, tetrabromocyclooctane is added to the styrene monomer. (TBC0) with a polymerization initiator. The styrene-based single system may, for example, be styrene, α-mercaptostyrene, p-methylstyrene, t-butylstyrene or chlorinated styrene. These monomers may be used singly or in combination of two or more. Among them, styrene is particularly preferred. Further, it may be combined with an acrylic acid or a mercapto acrylate such as methacrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate or cetyl methacrylate, or acrylonitrile or dimethyl. A monomer such as fumarate or ethyl fumarate is copolymerized with a styrene monomer. Further, a bifunctional monomer such as divinyl q benzene or alkylene glycol dimethacrylate may be copolymerized with a styrene monomer. The TBCO is used in an amount of from 0.45 to 2,000 parts by weight based on 100 parts by weight of the styrene monomer. Within this range, it is possible to ensure flame retardancy and heat fusion during molding, and it is possible to suppress coarse bubbles. The polymerization initiator is not particularly limited, and a polymerization initiator suitable for the polymerization temperature can be appropriately selected. For example, benzoquinone peroxide, laurel peroxide, tert-butyl peroxybenzoate, tert-butyl peroxytrimethylacetate, tert-butyl peroxydicarbonate, and peroxyacetic acid Tributyl ester, 2, 2-two 7 320897 200934814 (t-butylperoxy) butane, tert-butylperoxy-3,3,5-tridecylcyclohexanoate, di-tert-butyl An organic peroxide such as hexahydrophthalic acid phthalate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane or azobisisobutyronitrile or azobis An azo compound such as dimercaptophthalonitrile. These polymerization initiators can be used singly or in combination of two or more. The polymerization initiator may be used in an amount of from 0.05 to 3.0 parts by weight based on 100 parts by weight of the styrene monomer. The TBCO is dissolved in a styrenic monomer to give a monomer mixture. The monomer mixture may also contain a flame retardant aid. Examples of the flame retardant auxiliary include cumyl hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, and 2,3-dimethyl-2, 3-diphenylbutane. 5重量份。 0. 1 to 0. 5 parts by weight. The monomer mixture is dispersed in an aqueous medium and supplied to suspension polymerization. The aqueous medium may, for example, be water or a mixture of water and a water-soluble organic medium (e.g., decyl alcohol, ethanol). The aqueous medium may also contain additives such as surfactants, dispersing agents and the like. The surfactant may, for example, be an anionic surfactant, a cationic surfactant, an amphoteric ionic surfactant or a nonionic surfactant. Examples of the anionic surfactant include fatty acid oils such as sodium oleate and castor oil, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and alkyl groups such as sodium dodecylbenzenesulfonate. Benzene sulfonate, alkylnaphthalene sulfonate, alkane sulfonate, dialkyl sulfosuccinate, alkyl phosphate, naphthalene fumarate condensate, polyoxyethylene phenyl sulfonate S Salt, polyoxygen 8 320897 200934814 ethylene alkyl sulfate salt and the like. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and polyoxysorbitol fatty acid ester. Polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene-oxypropylene block polymer, and the like. The cationic surfactant may, for example, be an alkylamine salt such as laurylamine acetate or stearylamine acetate or a quaternary ammonium salt such as lauryl trimethylammonium chloride. The zwitterionic surfactant may, for example, be oxidized lauryl dimethylamine or a phosphate ester or phosphite surfactant. These surfactants can be used individually or in combination of 2 or more types. The surfactant may be used in an amount of from 0.002 to 1.0 part by weight based on 100 parts by weight of the aqueous medium. Examples of the dispersing agent include water-soluble polymers such as polyvinyl alcohol, mercapto cellulose, polyvinylpyrrolidone, and polydecylamine, magnesium pyrophosphate, triammonium phosphate, and refractory inorganics such as gems. Salt and so on. These dispersing agents can be used singly or in combination of two or more. The dispersing agent is used in an amount of from 0.2 to 10 parts by weight based on 100 parts by weight of the styrene monomer. A styrene single system is supplied to the suspension polymerization. The suspension polymerization is generally carried out at 50 to 120 ° C for 1 to 20 hours. As a result of the suspension polymerization, styrene resin particles can be obtained. Further, in the suspension polymerization or suspension polymerization, a physical foaming agent is impregnated with styrene resin particles to obtain a flame retardant expandable styrene 9 320 897 200934814 type resin particle. Here, the impregnation temperature at the time of impregnation can be adjusted to the rib to °C. By adjusting, it is possible to provide a flame-retardant foaming stupid eucalyptus tree, which can control the bubble diameter, and when there is no bubble coarseness during foaming, the thermal fusion property is good. Molding is carried out in a suspension polymerization in which the physical foaming agent is impregnated with styrene resin particles, and the physical foaming agent can be pressed into an aqueous medium. Further, when the physical foaming agent is impregnated with the stupid ethylene resin particles after the polymerization, the styrene resin particles may be taken out and impregnated, or may be impregnated with water: 〇 physical foaming agent means no Decomposed to directly have a foaming functional agent' corresponds to a so-called volatile blowing agent. The physical foaming agent may, for example, be an aliphatic hydrocarbon such as propane, n-butyl bromide, isobutyl orthognathic acid, orthofluorene, isovalerone or hexazone. These physical foaming agents may be used alone or in combination of two or more. 0咖。 The 敎 秘 纽 纽 纽 纽 纽 _ _ _ _ _ _ _ _ _ _ _ _ _ _ The granules and the flame-retardant foaming styrene-based resin particles are formed into a foamed molded body by a known pre-foaming step and a foam forming step. When Yulong is doubled, the average bubble of the bubbles constituting the foamed molded body can be in the range of 50 to 35 G_. In this range, the thermal fusion property of the foamed molded foam particles is good. Hair: Possibility = can also provide a flame retardant hair obtained by the above method. The flame retardant foaming = the four desert ring plums contained in the surface of the seed =:) The content of the four deserts contained in the whole particle is b (weight 320897 10 200934814 % to satisfy the formula 1. lxb The relationship between the two methods includes four deserts and Xin Xing. To satisfy this relationship, it is possible to provide both flame retardant and heat-melting properties, both of which are difficult to burn. The relationship is represented by the formula "1. 05xb. Here, the tetrabromocyclooctane content rate a' contained in the surface layer portion of the particle is difficult to directly measure, so the value measured by the following method is used. A test piece having a thickness of 0.2 mm was cut out from the surface of the foamed Q molded body in which the flame-retardant expandable styrene-based resin particles were foamed 50 times. The surface of the foamed molded body was flame-retardant. The surface layer of the styrene-based resin particles is a state of the surface layer of the flame-retardant expandable styrene-based resin particles. The amount of tetrabromocyclooctane in the test piece is measured and calculated relative to the test piece. The ratio of the total weight gives the tetrabromocyclooctane content a (weight) contained in the surface layer portion of the particle. In addition, the details of the measurement method are described in the examples. The tetrabromocyclooctane content b contained in the entire particle means that it is produced as a flame retardant foamable styrene resin particle. The ratio of the amount of the tetrabromocyclooctane of the raw material to the styrene is given. [Examples] The present invention is described in the following examples, but the present invention is not limited by the examples. The measurement method of the molecular weight, the volume expansion ratio, the foaming number, the flame retardancy, the average cell diameter, and the hot melt property of the styrene resin particles is described below. (The eighth resin of the ethylene resin particles) The weight average molecular weight (黯) was measured using a knee penetration analysis (趴), and the measurement method was as described in %. Further, the weight average molecular weight (five) means 320897 200934814 refers to the weight average molecular weight in terms of polystyrene (ps). The solution was dissolved in tetrahydrofuran (THF), 10 ml, and filtered through a non-aqueous 0.45 disk, and then analyzed by chromatography. The conditions of the chromatographic analysis were as follows. Liquid chromatography: Tosoh Corporation, trade name " Gel permeation chromatography analysis HLC -8020" Column: manufactured by Tosoh Corporation, trade name "TSKgel GMH-XL-L" 0 7.8mmx30cmx2 Branch column temperature: 40°C Carrier gas: tetrahydrofuran (THF) Carrier gas flow rate: 1 ml/min injection pump temperature: 35 ° C Detection: RI injection amount: 1 〇〇 microliters of the calibration line with standard polystyrene: manufactured by Showa Denko, the trade name "shodex" Weight average molecular weight: 103000 〇 and T〇s〇h company: Weight average Molecular weight: 5480000, 3840000, 355000, 102〇〇〇, 37900, 9100, 2630, 870 (volume expansion ratio) The volume expansion ratio is such that the preliminary expanded particles are naturally dropped in the measuring cylinder as a sample, and then the bottom of the measuring cylinder is tapped. Make the sample volume a certain amount and calculate according to the following formula. Such as stupid eucalyptus tree volume expansion factor (times) = sample volume in the measuring cylinder (mi) / sample quality 320897 12 200934814 quantity (g) x resin specific gravity (foaming multiple) expansion ratio is 3 The size and mass of the test piece (for example, 50×50×25 mm) of the foamed molded article were measured in the following manner, and were calculated according to the following gas. 0。 The specific gravity of the resin is 1.0. Foaming multiple (times) = test piece volume (cm3) / test test mass (§) ><resin specific gravity (flame retardancy) Ο The test piece was cut from the foamed molded body by a thickness of l〇mm, a length of 200 mm, and a width. 25 min 5 pieces 'The test piece is given the specified fire limit line and the combustion limit line. The test piece was burned with a wax crucible to the ignition limit line, and then left the flame, and the time (seconds) from the moment to the extinction of the flame was measured. The time (in seconds) until the flame is extinguished is not more than 3 seconds on the average of the test number 5, and no one exceeds the burn limit line and the burner passes. When the length of the flame is 150mm or more and the thickness is about 7mm or more, the length of the flame is about 1 mm. (Average bubble diameter) The foamed molded body was cut, and the inside of the cut surface of the cut surface was expanded by 1×1 to 9/10 or more by a scanning electron microscope (S-3000N, manufactured by Hitachi, Ltd.). And take photography. The four images of the captured images were printed on A4 paper, and the average chord length (t) of the bubbles was calculated from the number of bubbles on any one of the straight lines (length 6 〇 mm) according to the following formula. However, the 'arbitrary straight line avoids the contact of the milk bubble with the contact point as much as possible (the number of bubbles of the contact is calculated at the time of contact). The measurement system is 6 places. 13 320897 200934814 Average chord length t=60/ (number of bubbles 倍 photo magnification) Then, the bubble diameter D is calculated according to the following formula. D=t/0.616 (Hot-melting property) After the molding, the foamed molded body was dried at 70 t for 48 hours, and then cut to a thickness of about 5 mm in the vicinity of the center of the thickness direction using a nickel-chromium alloy slicer's 350×450×50 mm. The plate-shaped molded product is cut in half at the center in the longitudinal direction. The ratio (%) of the particles to the whole particles in which the expanded particles themselves were cut out in the entire particle of the cross section was calculated. The melting ratio of 8〇% or more is ◎, the melting ratio of 60 1 is less than 〇, and the melting ratio of 4〇 to less than 6〇% is △' less than 40% of the melting ratio is χ. Example 1 in a 100 liter high pressure pin,
反應終了後，冷卻至室 供給至離心分離步驟之 司製TCP-10)追加添入懸浮液中。 溫（25 C)，從高壓鋼取出内容物， kg的離子交換水 工業製藥公司製Pyr〇 12〇g、過氧化苯甲醯 〇 320897 14 200934814 後’使之乾燥而得到苯乙烯類樹脂粒子。 使所得到之苯乙烯類樹脂粒子分級成〇 6至〇. 7mm的 粒子。 於5升之尚壓鍋中饋入20〇〇g之水、9g之焦磷酸鎂及 0. 3g之十二烷基苯磺酸鈉，作為水性介質，再加入2〇〇〇g 之上述粒子而以30Orpm進行授拌。 然後，升溫至95。(：，一邊維持此溫度一邊壓入180g 之丁烷，含浸於粒子3小時’其後，藉冷卻以得到發泡性 〇苯乙烯類樹脂粒子。所得到之發泡性苯乙烯樹脂粒子於15 °C下放置4日使之熟成後，供給至預備發泡步驟。預備發 泡步驟之條件係將發泡性苯乙烯類樹脂粒子投入於預備發 泡機中，使用水蒸氣而使之預備發泡。藉此預備發泡得到 體積發泡倍數50倍之預備發泡粒子。將所得到之預備發泡 粒子的截面SEM照片（掃描型電子顯微鏡）表示於第i圖 中。從第1圖在實施例1中可知得到氣泡的粗密經控制之 0 預備發泡粒子。 進一步使預備發泡粒子在常溫下放置24小時使之熟 成，填充於公知之發泡聚苯乙烯用蒸氣成形機的模穴内， 以0· 6kg/cm G之水蒸氣加熱3〇秒鐘，水冷2〇秒鐘，可得 到300x450x100mm的發泡倍數5〇倍之嵌段發泡成形體。 所得到之嵌段發泡成形體的難燃性、平均氣泡徑及熱 融著性記載於表1中。 實施例2 除了使四溴環辛烷量為4〇〇g以外，其餘與實施例1同 15 320897 200934814 樣做法而得到發泡成形體。 實施例3 除了使四溴環辛烷量為600g以外，其餘與實施例1同 樣做法而得到發泡成形體。將所得到之預備發泡粒子的截 面SEM照片表示於第2圖中。從第2圖在實施例3中可知 得到氣泡的粗密經控制之預備發泡粒子。 實施例4 除了使四溴環辛烷量為800g以外，其餘與實施例1同 樣做法而得到發泡成形體。 實施例5 除了使含浸溫度變更為80°C以外，其餘與實施例2同 樣做法而得到發泡成形體。 實施例6 除了使含浸溫度變更為l〇〇°C以外，其餘與實施例2 同樣做法而得到發泡成形體。 實施例7 除了使含浸溫度變更為110°C以外，其餘與實施例2 同樣做法而得到發泡成形體。 實施例8 除了不添加過氧化二枯基以外，其餘與實施例3同樣 做法而得到發泡成形體。 實施例9 除了使用α -烯烴磺酸鹽2. 2g取代十二烷基苯磺酸鈉 以外，其餘與實施例5同樣做法而得到發泡成形體。 16 320897 200934814 實施例ίο 除了使含浸溫度為110°c以外，其餘與實施例9同樣 做法而得到發泡成形體。 實施例11 除了將磷酸三鈣係從大平化學公司製TCP-10變更為 Budenheim公司製C13-09以外，其餘與實施例2同樣做法 而得到發泡成形體。 實施例12 ® 除了不使用磷酸三鈣而使用焦磷酸鎂85g以外，其餘 與實施例2同樣做法而得到發泡成形體。 實施例13 除了不使用磷酸三鈣而使用焦磷酸鎂85g以外，其餘 與實施例3同樣做法而得到發泡成形體。 比較例1 除了使四溴環辛烷量為80g以外，其餘與實施例1同 0 樣做法而得到發泡成形體。 比較例2 除了使四溴環辛烷量為160g以外，其餘與實施例1同 樣做法而得到發泡成形體。 比較例3 除了使含浸溫度為115°C以外，其餘與實施例2同樣 做法而得到發泡成形體。 比較例4 除了使四溴環辛烷量為1200g以外，其餘與實施例1 17 320897 200934814 同樣做法而得到發泡成形體 截面娜照片表示於第3圖中第=備發泡粒子的 知因難燃劑之使用量多，故氣泡變小/在比較例4中可 比較例5 做法===_外’其餘與實施例1同樣 分級成使所得到之笨一子After the completion of the reaction, the mixture was cooled to a chamber and supplied to the centrifugation step, TCP-10), and added to the suspension. At room temperature (25 C), the contents were taken out from the high-pressure steel, and the ion exchange water of kg was made of Pyr〇 12〇g, benzophenone oxime 〇 320897 14 200934814, and dried to obtain styrene resin particles. The obtained styrene-based resin particles were classified into particles of 〇 6 to 〇. 7 mm. Feeding 20 〇〇g of water, 9 g of magnesium pyrophosphate and 0.3 g of sodium dodecyl benzene sulfonate in a 5 liter still pressure cooker as an aqueous medium, and adding 2 〇〇〇g of the above particles The mixture was mixed at 30 rpm. Then, the temperature is raised to 95. (: While holding this temperature, 180 g of butane was introduced and impregnated with the particles for 3 hours', and then cooled to obtain expandable styrene-based resin particles. The obtained expandable styrene resin particles were obtained at 15 After being aged for 4 days at ° C and then aging, it is supplied to a preliminary foaming step. The conditions of the preliminary foaming step are to introduce the foamable styrene resin particles into a preliminary foaming machine, and to prepare them by using steam. The foam was prepared by preliminary foaming to obtain a preliminary expanded particle having a volume expansion ratio of 50. The cross-sectional SEM photograph (scanning electron microscope) of the obtained preliminary expanded particle is shown in Fig. 1. In Example 1, it was found that the coarsely-predicted 0-prepared expanded particles of the bubbles were obtained. Further, the preliminary expanded particles were allowed to stand at room temperature for 24 hours to be cooked, and filled in a cavity of a known steam-forming machine for expanded polystyrene. The mixture was heated in water vapor of 0·6 kg/cm G for 3 seconds, and water-cooled for 2 seconds to obtain a block foam molded body having a foaming ratio of 5× times of 300×450×100 mm. Flame retardant, average The bubble diameter and the heat-melting property are shown in Table 1. Example 2 A foam molded article was obtained in the same manner as in Example 1 except that the amount of tetrabromocyclooctane was 4 〇〇g. Example 3 A foamed molded article was obtained in the same manner as in Example 1 except that the amount of tetrabromocyclooctane was 600 g. The cross-sectional SEM photograph of the obtained preliminary expanded particles is shown in Fig. 2. From the second In the same manner as in Example 1, except that the amount of tetrabromocyclooctane was 800 g, the foamed molded article was obtained in the same manner as in Example 1. 5 A foamed molded article was obtained in the same manner as in Example 2 except that the impregnation temperature was changed to 80 ° C. Example 6 The same procedure as in Example 2 was carried out except that the impregnation temperature was changed to 10 ° C. The foamed molded article was obtained. Example 7 A foam molded article was obtained in the same manner as in Example 2 except that the impregnation temperature was changed to 110 ° C. Example 8 Except that the dicumyl peroxide group was not added, the same was carried out. Example 3 is the same A foamed molded article was obtained. Example 9 A foam molded product was obtained in the same manner as in Example 5 except that the α-olefin sulfonate 2.2 g was used in place of sodium dodecylbenzenesulfonate. 16 320897 200934814 Example: A foamed molded article was obtained in the same manner as in Example 9 except that the impregnation temperature was changed to 110 ° C. Example 11 In addition to changing the tricalcium phosphate system from TCP-10 manufactured by Daping Chemical Co., Ltd. to C13 manufactured by Budenheim Co., Ltd. A foamed molded article was obtained in the same manner as in Example 2 except for -09. Example 12 ® A foamed molded article was obtained in the same manner as in Example 2 except that 85 g of magnesium pyrophosphate was used without using tricalcium phosphate. (Example 13) A foamed molded article was obtained in the same manner as in Example 3 except that 85 g of magnesium pyrophosphate was used without using tricalcium phosphate. Comparative Example 1 A foam molded article was obtained in the same manner as in Example 1 except that the amount of tetrabromocyclooctane was 80 g. Comparative Example 2 A foamed molded article was obtained in the same manner as in Example 1 except that the amount of tetrabromocyclooctane was changed to 160 g. Comparative Example 3 A foamed molded article was obtained in the same manner as in Example 2 except that the impregnation temperature was changed to 115 °C. Comparative Example 4 A photograph of a cross section of a foamed molded article obtained in the same manner as in Example 1 17 320897 200934814 except that the amount of tetrabromocyclooctane was 1200 g was shown in Fig. 3 The amount of the flammable agent used was large, so the bubble became small. In Comparative Example 4, the comparative example 5 was practiced ===_ outside. The rest was classified in the same manner as in Example 1 to obtain a stupid one.
在綱：之麟下，於水性介質中加入他之四漠環 將二!^ 餘與實施例1同樣做法而得到發泡成形體。 Γ = 泡粒子的截面SEM照片表示於第4圖 /第4圖在比較例5中，可知難燃劑多存在於表層部， :層部的氣泡小’中心之氣泡變大，於氣泡產生粗密。 比較例6 、除了不添加四如哀辛燒量以外，其餘與實施例丄同樣 ^法而得·乙_練子。使所得狀苯㈣樹脂粒子 刀級成0. 6至0. 7丽的粒子。In the same manner as in Example 1, a foamed molded body was obtained by adding the same to the aqueous medium. Γ = SEM photograph of the cross section of the blister particles is shown in Fig. 4/4. In Comparative Example 5, it is understood that the flame retardant is present in the surface layer portion, and the bubble at the center of the layer is small, and the bubble at the center becomes large. . Comparative Example 6 was the same as the Example 丄 except that no four such as sorrow was burned. 5至的颗粒。 The benzene particles of the benzene (4) granules.
在300rpm之攪拌下，於水性介質中加入3〇g之四溴環 辛烷以外，其餘與實施例1同樣做法而得到發泡成形體。 將所得到之預備發泡粒子的截面SEM照片表示於第5圖 中。從第5圖在比較例6中，可知難燃劑多存在於表層部， 故表層部的氣泡小，中心之氣泡變大，於氣泡產生粗密。 於實施例2至13及比較例1至6所得到之嵌段發泡成 形體的難燃性、平均氣泡徑及熱融著性記載於表1中。 18 320897 200934814 [表1]A foamed molded article was obtained in the same manner as in Example 1 except that 3 〇g of tetrabromocyclooctane was added to the aqueous medium under stirring at 300 rpm. A cross-sectional SEM photograph of the obtained preliminary expanded particles is shown in Fig. 5. In Comparative Example 6, it can be seen that the flame retardant is present in the surface layer portion in the fifth embodiment. Therefore, the bubbles in the surface layer portion are small, and the bubbles in the center are large, and the bubbles are coarse. The flame retardancy, average cell diameter, and hot meltability of the block foamed articles obtained in Examples 2 to 13 and Comparative Examples 1 to 6 are shown in Table 1. 18 320897 200934814 [Table 1]
t B C 0 份 分散劑 界面活性劑 含浸 溫度 ν 分子量 Mw 難燃性 秒 平均 氣泡 徑 u m 熱 融 接 性 實 施 例 1 ο. 5 TCP-10 十二烷基苯磺酸鈉 95 265000 1. 7 及格 加ό (S) 2 Ι.ό TCP-10 十二烷基苯磺酸鈉 05 2&6000 1· 1 及格 290 (S) 3 1. S TCP-10 十二烷基苯磺酸鈉 246000 0. 3 及格 170 0 4 2. 0 TCP-1-0 十二烷基苯磺酸鈉 分5 228000 0. 3 及格 180 0 5 1.0 TCP-10 十二烷基苯磺酸鈉 80 268000 0· 6 及格 340 ◎ 6 1.0 TCP-10 十二烷基笨績酸鈉 100 247000 0.9 及格 180 0 7 1.0 TCP-10 十二烷基苯績酸鈉 110 241000 1.0 及格 73 0 8 1. 5 TCP-10 十二烷基苯磺酸鈉 95 252000 0.6 及格 210 U 9 1. 0 TCP-io α-烯烴磺酸里 239000 0· 5 及格 100 0 1 0 1· 0 TCP-10 α-烯烴績酸里 ϋό 237000 0.3 及格 110 0 11 1. 0 C13-09 十二烷基苯磺酸鈉 95 252000 0.6 及格 220 0 1 2 i. ο 焦磷酸鎂 十二烷基苯磺酸鈉 合5 248000 0.4 及格 270 ◎ i ΰ 1. 5 焦磷酸鎂 十二烷基苯磺酸鈉 95 251000 0. 3 及格 250 0 比 較 例 1 0· 2 TCP-10 十二烷基苯磺酸鈉 283000 燃燒 不及格 450 (Q) 2 ο. 4 TCF-10 十二烷基苯磺酸鈉 95 如 ιόόό 3. 7 不及格 350 <3) 3 1. 0 TCP-10 十二規*基苯續酸納 ιιδ 223000 1. 3 及格 41 X 4 3. 0 TCP-10 十二烷基苯磺酸鈉 05 191000 0.3 及格 35 X 5 0. 5 TCP-10 十二烷基苯磺酸鈉 9S 262000 3. 3 不及格 320 0 6 1. 5 TCP-10 十二烷基苯績酸鈉 96 224000 0.8 及格 150 X 從上述表1 ’可知能提供一種發泡性苯乙烯類樹脂粒 子，其係使用特定量之特定難燃劑，使物理發泡劑之含浸 溫度為特定溫度，可得到發泡時粒子間之熱融著性優異， 同時具有優異之難燃性之發泡成形品。 以如下之方法測定實施例1至13及比較例1至6所得 到之發泡性苯乙烯類樹脂粒子的表層部及粒子全體的四溴 環辛烷含有率，其結果表示於表1。 (四溴環辛烷含有率測定方法） 19 320897 200934814 以切片機（富士島工機社製FK-4N)將50倍發泡成型品 的表面部分裁切成厚0. 2mm、長20cm、寬20cm之片，再處 理作為難燃性發泡性苯乙烯類樹脂粒子表層部。實施被切 片之表面部分的四溴環辛烷含有率的測定。四溴環辛烷含 有率的測定係使用螢光X線分析裝置（Rigaku公司製RIX-2100)而藉級數分析法（薄膜法）而測定。亦即，使所裁切之 表面部分2至3g在200至230°C中進行熱壓而製作厚0. 1 至1丽、長5cm、寬5cm之薄膜。測定薄膜之重量後，算出 單位面積重量，使平衡成分為C8H8，使Br量從X線強度以 ❹ 級數分析法算出。四溴環辛烷中所含有的Br之比率為 75°/◦，故從所得到之Br量算出薄膜中之四溴環辛烷量。使 算出結果作為難燃性發泡性苯乙烯樹脂粒子的表層部所含 有之四溴環辛烷含有率。難燃性發泡性苯乙烯樹脂粒子的 全體所含有之四溴環辛烷含有率係與四溴環辛烷含浸時之 饋入量相同。 難燃性發泡性苯乙烯樹脂粒子的表層部與全體中所含 ^ ❹ 有之四溴環辛烷含有率、表層部所含有之四溴環辛烷含有 率對全體含有之四溴環辛烷含有率之比表示於表2中。 20 320897 200934814 [表2] 全體之TBCO 含有率b (wt%) 表層却之 TBC0含有率a (wt%) TBCO含有率之 表層部/全體比 b X 1. Τ' 實施例1 υ. 5 0 0. 4 9 0 . 9 8 0. ~~~ 貧施例2 1. 0 0 1 · 0 1 1 . 0 1 1 . 1 — [施例3 丄. 5 0 1 . 5 2 1 . 0 1 1 . 6 5 貧施例4 2 . 0 0 2 . 0 1 1 . 0 1 2. 2 貧施例5 1 . 0 0 \ 0. 9 9 0. 9 9 1· 1 ' 實施例6 1 . 0 0 1 . 0 3 1 . 0 3 1.1 — 實施例7 1 . 0 0 1 . 0 1 1 . 0 1 1. 1 實施例8 1 . 5 0 1. 5 0 1 . 0 0 1 - 6 5 實施例9 1 . 0 0 1. 0 1 1 . 0 1 1 . 1 實施例1 0 1. 0 0 1.00 1 . 0 0 1 . 1 實施例1 1 1 . 0 0 1 . 0 0 1 . 0 0 1 . 1 實施例1 2 1. 0 0 0. 9 9 0. 9 9 1 . — — 1 實施例1 3 1. 5 0 1. 5 5 1. 0 3 1 . 6 5~ 比較例1 0. 2 0 0. 2 0 1.0 0 0. 2 2 比較例2 0. 4 0 0. 4 1 1 . 0 1 0. 4 4 ~ 比較例3 1 . 0 0 1.01 1 . 0 1 1. 1 比較例4 3. 0 0 2. 9 5 0. 9 8 3. 3 比較例5 0. 5 0 0. 5 6 1 . 12 0. 5 5~~~ 比較例6 1 . 5 0 1 . 7 1 1 . 14 1. 6 5 從表2 ’可知在滿足式a $ 1. 1 xb之實施例中，可提供 一種發泡性苯乙烯類樹脂粒子，其係可得到發泡時粒子間 之熱融著性優異’同時具有優異之難燃性之發泡成形品。 另外’不滿足上述式1· lxb之比較例5及6係可知發泡 成型σσ之熱融著性及/或難燃性差。 【圖式簡單說明】 第1圖係實施例1之預備發泡粒子的截面之電子顯微 鏡照片。 第2圖係實施例3之預備發泡粒子的截面之電子顯微 鏡照片。 21 320897 200934814 第3圖係比較例4之預備發泡粒子的截面之電子顯微 鏡照片。 第4圖係比較例5之預備發泡粒子的載面之電子顯微 鏡照片。 第5圖係比較例6之預備發泡粒子的截面之電子顯微 鏡照片。 【主要元件符號說明】 無。 ❿t BC 0 parts dispersant surfactant impregnation temperature ν molecular weight Mw flame retardancy second average bubble diameter um heat fusion example 1 ο. 5 TCP-10 sodium dodecyl benzene sulfonate 95 265000 1. 7 ό (S) 2 Ι.ό TCP-10 Sodium dodecyl benzene sulfonate 05 2 & 6000 1· 1 Pass 290 (S) 3 1. S TCP-10 Sodium dodecyl benzene sulfonate 246000 0. 3 Passing 170 0 4 2. 0 TCP-1-0 Sodium dodecyl benzene sulfonate 5 228000 0. 3 Passing 180 0 5 1.0 TCP-10 Sodium dodecyl benzene sulfonate 80 268000 0· 6 Pass 340 ◎ 6 1.0 TCP-10 Dodecyl stupid sodium 100 247000 0.9 Passing 180 0 7 1.0 TCP-10 Sodium dodecyl benzoate 110 241000 1.0 Passing 73 0 8 1. 5 TCP-10 Dodecyl benzene Sodium sulfonate 95 252000 0.6 Passing 210 U 9 1. 0 TCP-io α-olefin sulfonic acid 239000 0· 5 Passing 100 0 1 0 1· 0 TCP-10 α-olefin acid acid ϋό 237000 0.3 Passing 110 0 11 1. 0 C13-09 sodium dodecyl benzene sulfonate 95 252000 0.6 pass 220 0 1 2 i. ο magnesium pyrophosphate sodium dodecyl benzene sulfonate 5 248000 0.4 pass 270 ◎ i ΰ 1. 5 pyrophosphate Magnesium dodecyl Sodium sulfonate 95 251000 0. 3 Passing 250 0 Comparative Example 1 0· 2 TCP-10 Sodium dodecyl benzene sulfonate 283000 Burning failure 450 (Q) 2 ο. 4 TCF-10 Dodecyl benzene sulfonic acid Sodium 95 such as ιόόό 3. 7 failing 350 <3) 3 1. 0 TCP-10 12 gauge* benzene benzoate ιιδ 223000 1. 3 Passing 41 X 4 3. 0 TCP-10 Dodecylbenzene Sodium sulfonate 05 191000 0.3 Passing 35 X 5 0. 5 TCP-10 Sodium dodecyl benzene sulfonate 9S 262000 3. 3 Failed 320 0 6 1. 5 TCP-10 Sodium dodecyl benzoate 96 224000 0.8 Passage 150 X From the above Table 1 ', it can be understood that a foamable styrene resin particle can be provided by using a specific amount of a specific flame retardant, and the impregnation temperature of the physical foaming agent is a specific temperature, and foaming can be obtained. A foam molded article excellent in thermal fusion between particles and excellent in flame retardancy. The surface layer portion of the expandable styrene resin particles obtained in Examples 1 to 13 and Comparative Examples 1 to 6 and the tetrabromocyclooctane content of the entire particles were measured in the following manner. The results are shown in Table 1. The thickness of the surface of the 50-fold foamed molded article was cut into a thickness of 0. 2 mm, a length of 20 cm, and a width by a slicer (FK-4N, manufactured by Fujishima Kogyo Co., Ltd.). A sheet of 20 cm was further treated as a surface layer portion of a flame retardant expandable styrene resin particle. The measurement of the tetrabromocyclooctane content of the surface portion of the cut piece was carried out. The measurement of the content of tetrabromocyclooctane was measured by a series analysis method (film method) using a fluorescent X-ray analyzer (RIX-2100, manufactured by Rigaku Co., Ltd.). That is, the cut surface portion 2 to 3 g was heat-pressed at 200 to 230 ° C to form a film having a thickness of 0.1 to 1 liter, a length of 5 cm, and a width of 5 cm. After measuring the weight of the film, the basis weight was calculated so that the equilibrium component was C8H8, and the amount of Br was calculated from the X-ray intensity by the ❹ series analysis method. Since the ratio of Br contained in tetrabromocyclooctane is 75 ° / Torr, the amount of tetrabromocyclooctane in the film is calculated from the amount of Br obtained. The calculated result is the tetrabromocyclooctane content of the surface layer portion of the flame retardant expandable styrene resin particles. The tetrabromocyclooctane content of the flame-retardant expandable styrene resin particles is the same as that of the tetrabromocyclooctane impregnation. The content of the tetrabromocyclooctane contained in the surface layer portion and the entire surface of the flame-retardant expandable styrene resin particles and the tetrabromocyclooctane content in the surface layer portion are tetrabromocyclooctane contained in the entire surface. The ratio of the alkane content ratio is shown in Table 2. 20 320897 200934814 [Table 2] TBCO content rate b (wt%) of the whole TBC0 content rate of the surface layer a (wt%) Surface layer/total ratio of the TBCO content rate b X 1. Τ' Example 1 υ. 5 0 0. 4 9 0 . 9 8 0. ~~~ Poor Example 2 1. 0 0 1 · 0 1 1 . 0 1 1 . 1 — [Example 3 丄. 5 0 1 . 5 2 1 . 0 1 1 6 5 Poor Example 4 2 . 0 0 2 . 0 1 1 . 0 1 2. 2 Poor Example 5 1 . 0 0 \ 0. 9 9 0. 9 9 1· 1 ' Example 6 1 . 0 0 1 . 0 3 1 . 0 3 1.1 — Example 7 1 . 0 0 1 . 0 1 1 . 0 1 1. 1 Example 8 1 . 5 0 1. 5 0 1 . 0 0 1 - 6 5 Example 9 1 . 0 0 1. 0 1 1 . 0 1 1 . 1 Example 1 0 1. 0 0 1.00 1 . 0 0 1 . 1 Example 1 1 1 . 0 0 1 . 0 0 1 . 0 0 1 . Example 1 2 1. 0 0 0. 9 9 0. 9 9 1 . - 1 1 Example 1 3 1. 5 0 1. 5 5 1. 0 3 1 . 6 5~ Comparative Example 1 0. 2 0 0 2 0 1.0 0 0. 2 2 Comparative Example 2 0. 4 0 0. 4 1 1 . 0 1 0. 4 4 ~ Comparative Example 3 1 . 0 0 1.01 1 . 0 1 1. 1 Comparative Example 4 3. 0 0 2. 9 5 0. 9 8 3. 3 Comparative Example 5 0. 5 0 0. 5 6 1 . 12 0. 5 5~~~ Comparative Example 6 1 . 5 0 1 . 7 1 1 . 14 1. 6 5 from Table 2 'in the example that satisfies the formula a $ 1. 1 xb Further, it is possible to provide a foamable styrene-based resin particle which is excellent in heat-melting property between particles during foaming and which has excellent flame retardancy. Further, in Comparative Examples 5 and 6 which did not satisfy the above formula 1·lxb, it was found that the heat-melting property and/or the flame retardancy of the foam molding σσ were poor. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an electron micrograph of a cross section of the preliminary expanded particles of Example 1. Fig. 2 is an electron micrograph of a cross section of the preliminary expanded particles of Example 3. 21 320897 200934814 Fig. 3 is an electron micrograph of a cross section of the preliminary expanded particles of Comparative Example 4. Fig. 4 is an electron micrograph of the surface of the preliminary expanded particles of Comparative Example 5. Fig. 5 is an electron micrograph of a cross section of the preliminary expanded particles of Comparative Example 6. [Main component symbol description] None. ❿
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