經濟部中央標準局員工消費合作杜印裝 ^ ^ 6 u 1 A7 _B7__ 五、發明説明（丨） 本發明偽有颶於一種具有良好難燃性、高耐熱性，並 且具有®異面衝擊強度、抗氣鼸燒痕及成型品外觀優良等 性質之雞燃性苯乙烯条樹脂組成物。 苯乙烯糸樹脂在日常生活中己有很廣泛的蓮用，特別 是在家電用品及商業機械上，例如錄放影機、電視機、電 腦、打字機等之外殼，即多由苯乙烯条樹脂所製。雖然這 些樹脂製品具有價格低廉、重量輕、且具備適當機械強度 等優黏，但與金屬相比較，其缺點便在於樹脂具易燃性. 因此，在一些火災事故中不乏因樹脂製品的易燃性，而導 致重大傷害之例，正因如此，難燃性在樹脂工業技術上一 直是項極為重要的課題。 一般而言，為了使樹脂製品具有難燃待性之方式有二 ,其一是將具有反應性的雞燃性物質與反應單體混入樹脂 中，一起進行聚合反應，以賦予最终樹脂製品雞燃持性， 此種方法較常使用在熱固性樹脂上，另一種方式則是將非 反應性的難燃物質和樹脂本鼸利用例如押出機等之混練装 置予以充份混合練製，而使得樹脂具有雞燃待性，此法較 常使用在熱可塑性樹脂。 而為了賦予苯乙烯糸樹脂難燃持性，在習知技術中常 用的難燃劑一般是靥於含窗素的有機雞燃劑，尤其是含氛 或含溴的有機難燃劑，例如十溴二苯基»(和031)1'〇111〇(^口-heny 1 〇x i de)、八澳二苯基醚（〇c tabromod i pheny 1 ox i de )、四漠雙 SSA (tetrabromobisphenyl A)、雙（二漠苯氣） 乙院[bis(t「ibronophenoxy) ethane]、1,2-雙（四澳软醯 第03頁 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） ---------装------ΪΤ------# (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作杜印製 Q - r c ' ,f A/ 〇〇〇〇〇_[ _b7__ 五、發明説明（二） 亞胺基）乙院[ethylene bis(tetrab「〇B〇phthalinide)] 、雙（六«琛戊二 :嫌）琢辛院[bis(hexachlor〇-cyclopent-adiene) cyclooctane]、十澳二苯基甲院、十漠二苯基乙 烷等；逭些難燃劑在使用上通常配合適當比例的無機難燃 助劑，以降低含鹵素有機物的使用量，以避免因含鹵素有 機雞燃_的添加降低了苯乙烯条樹脂的機械性質與耐熱性 質等原材料之物性。 另一方面，在苯乙烯糸樹脂中難燃劑的添加對原材料 的影響，以衝擊強度之破壤以及射出成型時在成型品表面 形成燒痕（Gas bU「nning)最為家電用品業及商業機器、電 子賫訊業所在意，當樹脂之衝擊強度不足時，會造成成型 品因間隙狀之網狀結構（散熱設計），而無法承受搬浬、安 装時的碰撞，甚至導致破裂、損壤，此外，在樹脂射出成 型時由於樹脂及難燃劑易裂化，而產生分解性的酸性物質 ，例如溴酸（HBr)、氫氯酸（HCI)等；尤其是對於近來經常 使用之Pin gate模具，因灌口 口徑滅少易產生更大的摩擦 熱，故於射出時，樹脂本身溫度的增加，會使得樹脂裂化 情況更加駸重，此亦會導致氣體的大量產生；上述生成的 揮發性分解物質（即前述溴酸、氫氮酸等），在冷卻後會在 成型品外表產生氣體燒痕，如此亦會影《成品之外觀，前 述缺失將使得樹脂之用途受到很大的限制。 例如.美國發明專利第3830766號案中t述及，以四 溴雙酚A作為難燃劑，且併用三氣化二銻、氱化聚乙烯等 難燃助劑之難燃性樹脂組成物可提高樹脂之延展性及抗老 第04頁 本紙張尺度適用中國國家標準（CNS ) A4规格（210 X 297公釐） 訂 各 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7_ 五、發明説明（3 ) 化性質，但是四溴雙酚A添加於苯乙烯条樹脂中時，明顯 會攢害到原材料的物性，例如耐熱性質、面衝擊強度等， 且射出成型品發生氣醱燒痕之情況亦無法獲得改菩，故在 使用上受到限制。 為了改善前述缺失，本案發明人經研究發現.在待定 之苯乙烯糸樹脂中配合含鹵素有機難燃劑，能播得良好之 難燃性與耐熱性，樹脂之面衝擊強度、外觀與抗氣醴燒痕 之難燃性苯乙烯糸樹脂組成物。 爱是，本發明之主要目的偽在提供一種具有良好之難 燃性、耐熱性，並且具有優異面衝擊強度、外觀及抗氣醱 燒痕之難燃性苯乙烯条樹脂組成物。 而，本發明之難燃性苯乙烯糸樹脂組成物，其主要包 含： (一）100重量份之苯乙烯条樹脂，其偽由： (1) 在重量平均粒徑0.05〜0.8湖之橡膠接枝共聚物 (A) 0.1〜10重量份、二烯糸橡膠2〜25重量份及丙烯基条 共聚物（B)0.1〜10重量份存在下，與基於總合100重量份 之下述單體：苯乙烯条單體80〜45重量份、丙烯腈条單體 15〜50重量份及可共聚合單醱〇〜40重量份進行塊狀及/或 溶液聚合而得之接枝共聚物（C) 2〜60重量份； (2) 在重量平均粒徑0.05〜0.8_之橡膠乳液50〜85 重量份存在下，與苯乙烯系單鱷、丙烯睛条單醱及視需要 而灌之可共聚合單«混合物50〜15重量份乳化接枝聚合而 得之接枝共聚物（D) 5〜60重置份； 第05頁 本紙張尺度適用中國國家揉準（CNS ) A4規格（21〇X297公釐） ---------批衣------1T------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 J__B7___ 五、發明说明（4·) (3)苯乙烯条單體80〜50重量份、丙烯腈糸單體20〜 50重量份及視需要而遘之可共聚合單體聚合〇〜40重量份 聚合而得之共聚物（E) 0〜80重量份； (二）5〜40重量份的溴含量40重量S!以上之含溴糸有 機難燃劑。 根據前述組成，邸可製得一同時具有良好難燃性、高 耐熱性，並且具有優異的面衝擊強度、抗氣疆燒痕，且成 型品外觀優良之難燃性苯乙烯条樹脂組成物。 本發明之橡膠接枝共聚物（A)僳由乳化聚合製得，較 佳的製造方法偽將二烯条單鼸及其他可共聚合單鳢直接以 乳化聚合法聚合成重置平均粒徑0.05〜0.8卿之橡膠乳液 ,亦可將前述單體以乳化聚合法製成0.05〜0.2挪之小粒 徑橡膠乳液後，再以冷凍肥大法或機械肥大法或添加劑肥 大法，將前述小粒徑橡謬乳液肥大成0.15〜0.8卿之橡嘐 乳液；其中，添加劑肥大法所使用之添加劑可為：醋酸酐 、氯化氫、硫酸等酸性物質，或為氛化納、氛化鉀、氛化 鈣等鹽基性物質，以及（甲基）丙烯酸条-(甲基）丙烯酸_ 条共聚物（如甲基丙烯酸-丙烯酸丁酯共聚物、甲基丙烯酸 -丙烯酸乙酯共聚物）等含羧酸基之高分子凝集劑。 將前述搛膠乳液50〜85重量份之苯乙烯条單體、丙浠 腈糸單醱50〜15重釁份、其他可共聚合單體0〜30重量份 ,以及適當的乳化剤與起始劑進行接枝聚合反應；上述起 始劑可使用技術上常見之起始劑，例如：二苯甲醛過氣化 物（di benzoyl peroxide)、二異丙基苯過氧化氫（diisop- 第06頁 本紙張尺度適用中國國家橾準（CNS ) A4规格（210X297公釐） ---------^------ΪΤ------# (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印11 A7 B7 五'發明説明（s) ropyl benzene hydroperoxide )、第三丁基遇氣化 ( tert-butyl hydroperoxide)、異丙苯化過氧化氦（cumene h y d r o p e r o x i d e)、過琉酸鉀（p o t a s s i u m p e r s u 1 f a t e )等 .其中又以有機過氣化氫類為佳。 本發明之橡騵接枝共聚物（A)在聚合時尚可使用氣化 還原催化条统之活化劑，或鐵離子等習知技術上的活化劑 ，例如焦碟酸銷右旋糖（sodium pyrophosphate dextrose )、甲薛次硫酸納（s o d i u π f o r in a 1 d e h y d e s u 1 f o x y 1 a t e)、 抗澳血酸（ascorbic acid)、二翔基丙掘（dihydroxy ace-tone)等皆可使用，此外.也可加上乙二胺四乙酸鹽（eth-y 1 e n e d i a B 丨 n e t e t r* a c e t i c a c i d s a 11 )促進其效果；而 鐵離子之來源可使用氰化鐵或碕酸亞鐵。 前述橡謬接枝共聚物（A)之接枝率可_由聚合反應條 件加以控制，例如：聚合溫度、起始两、乳化劑、鏈移轉 劑之用量及種類、單鳢之添加方法等加以控制；亦可依習 知技術添加鍵移轉劑來調整接枝共聚物（A)之分子量，常 見的鐽移轉劑有：正一丁基破醇（n-butyl nercaptan )、 正一辛基硫醇（n-octy丨nercaptan )、正--h二院基硫醇 (n-dodecyl uercaptan)、第三--h 二院基硫醇（te「t-do- decyl mercaptan);上述橡腰接枝共聚物（A)之分子量亦 可藉由聚合溫度、起始劑之種類及用量、單體之添加方法 等聚合條件之改變來調整，其接枝聚合之反應溫度在90Ό 以下，尤其在30〜80T之間較佳；接枝用單體可一次加入 ,也可分批加入，亦可連續加入或將各種單體分段接枝聚 第07頁 本紙张尺度遴用中國國家橾準（CMS ) A4规格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 、vs 經濟部中央標準局員工消费合作社印製 A7 B7 五、發明説明（t ) 合，如此即可得到橡膠接枝共聚物乳液；再將前述接枝共 聚物乳液經由傳統的凝結脱水、乾燥等步驟，來得到本發 明所需重量平均粒徑0.05〜0.8細之橡醪接枝共聚物（A)< 本發明之搛騵接枝共聚物（A)雖可蓮用前述各種方法 製得，但基於縮短橡膠乳液之聚合時間以提高製造效率之 原則，乃以肥大化法之橡膠乳液為佳，其中，基於肥大化 粒徑的均一性及減少凝結塊之目的，又以添加含羧酸基之 高分子凝集劑肥大化而成之橡膠乳液更佳。 本發明之橡膠接枝共聚物（A)所使用的苯乙烯条單體 可為苯乙烯、α —甲基苯乙烯、α— «苯乙烯、p-t-丁基苯乙烯、P —甲基苯乙烯、〇 -氰苯乙烯、P —氯笨 乙烯、2, 5 —二氱笨乙烯、3, 4 —二氱苯乙烯、2, 4, 6—三溴苯乙烯、2. 5—二溴笨乙烯等，其中，以 苯乙烯或α—甲基苯乙烯為佳。 而使用之丙烯腈条單體可為：丙烯腈、ct —甲基丙烯 8育等；其中以丙烯腈較佳。 本發明橡謬接枝共聚物（A)中使用之可共聚合單體可 為··（甲基）丙烯酸酯糸單醱、馬來醛亞胺糸單體等；其中 (甲基）丙烯酸酯糸單醴可為：甲基丙烯酸甲酯、甲基丙烯 酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸 苯甲酯、甲基丙烯酸己酯、甲基丙烯酸環己酯、甲基丙烯 酸十二酯、甲基丙烯酸2 _羥乙酯、甲基丙烯酸编水甘油 酯及甲基丙烯酸二甲氰基乙酯等，其中以甲基丙烯酸甲酯 較佳。 第08頁 本紙張尺度適用中國國家標準（CMS ) Α4規格（210 X 297公釐） ---------^------ΐτ------# (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（了） 馬來醯亞胺条單醴可為：馬來醒亞胺、N -甲基馬來醯 亞胺、N-異丙基馬來醯亞胺、N-丁基馬來睡亞胺、N-己基 馬來醯亞按、辛基馬來醢亞胺、N-十二基馬來醯亞胺、 N-琛己基馬來醛亞胺、N-苯基馬來醯亞胺、N-2,3-甲苯基 馬來醛亞胺、N-2,4-甲苯基馬來醯亞胺、N-2,3-乙苯基馬 來醯亞胺、N-2,4-乙笨基馬來醯亞胺、N-2,3-丁苯基馬來 醯亞胺、N-2, 4-丁苯基馬來醯亞胺、N-2,6-甲苯基馬來醯 亞胺、N-2,3-氛苯基馬來醛亞胺、N-2.4-氱苯基馬來醛亞 胺、N-2,3-溴苯基馬來醛亞胺、N-2,4-溴苯基馬來匿亞胺 等，其中又以N-甲基馬來酵亞胺為最佳。 本發明之丙烯基系共聚物（B)偽由：（甲基）丙烯酸酯 条單醱及丙烯腈条單醴中選出最少一種單鼸10〜1〇〇重量％ 、苯乙烯条單體0〜80重量，以及其他可共聚合單體0〜 30重量χ所組成；上述成份中的單體種類大致相同於橡膠 接枝共聚物（Α)中所載者，不同之處在於：丙烯基糸共聚 物（Β)中之其他可共聚合單腥不包含馬來醯亞胺条單體； 至於其聚合方式可葙由溶液、塊狀、乳液或懸浮等各種聚 合方式而得，其中以溶液或塊狀聚合法為佳。 本發明接枝共聚物（C)中使用之二烯糸橡膠乃為：二 烯糸單體成份經離子聚合後玻璃轉移溫度在-2〇t：以下之 聚合證，較佳之二烯条橡驂例如：丁二烯橡膠、異戊間二 烯橡醪、氰丁二烯橡膠等；其中，丁二烯橡膠有高順式（ Hi-Cis)含量及低順式（Lovj-Cis)含量之分；高順式橡謬中 ,其順式（Cis)/乙烯基（Vinyl)之典型重量組成為94〜98 第09頁 本紙張尺度適用中國國家標準（CNS ) A4规格（210X 297公釐） ---------^------ir------線. (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消费合作杜印製 A7 B7 五、發明説明（s ) %/1〜5%,其餘組成則為反式（Trans)結構；其Mooney 黏度在20〜120間，分子置範園以1〇〇,〇〇〇〜800,000為佳 ;低順式橡繆中，順式/乙烯基的典型重量組成範圍在20 〜40%/1〜20 %,其餘為反式結構，其Mooney黏度在20 〜120間，其他適合的橡膠材料尚有：丙烯睛橡謬、苯乙 烯/丁二烯橡膠，或是上述不同橡膠之混合；笨乙烯/丁 二烯橡膠邸俗稱的S B R。適合於本發明的苯乙烯/丁二 烯共聚合橡醪，其聚合型式可為二段式（di-block)共聚合 、三段式（tri-block)共聚合、無規則共聚物（random)或 星式共聚合（star type )。苯乙烯/ 丁二烯橡膠之重量比 例範圍較佳為5/100到80/20 ,分子量範圍較佳為50,000 〜600,000 ,上述適用於本發明之橡膠以丁二烯橡膠及笨 乙烯/丁二烯橡膠為佳.其中又以丁二烯橡謬更佳。 本發明之接枝共聚物（C)偽將橡醪接枝共聚物（A)0.1 〜10重量份、二烯条橡驂2〜25重量份、丙烯基糸共聚物 (B)0.1〜1〇重量份，以及總合100重置份之下述單鳢：苯 乙烯系單黼80〜4 5重鼉份、丙烯腈系單體15〜50重量份及 可共聚合單體0〜40重量份，以塊狀及/或溶液聚合法聚 合而得。 詳細而言，本發明偽將前述單醱與橡騵接枝聚合物（A )、二烯条橡膠、丙烯基糸共聚物（B),及依需要而選用 之溶劑混合溶解所成之原料溶液送入反應器中聚合；或者 將部份前述單黼、橡臞接枝聚合物（A)、丙烯基条共聚物 (B),及依需要而選用之溶劑混合溶解成一獨立之原料溶 第10頁 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） ---------1------IT------# (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作杜印¾ A7 B7 五、發明説明（7 ) 液，再將其餘的單體與二烯糸橡膠混合溶解成另一原料溶 液，二原料溶液分別送入反應器中聚合。 前述原料混合物可以在傳統具有高剪應力、高攪拌速 度的溶解槽中進行溶解，此溶解槽可使用：具有帶狀螵旋 式S拌葉、螺旋漿式贗拌蕖、或者其他可產生高剪應力之 «拌葉等，在足夠的時間下，可以將上述二烯糸橡膠或搛 謬接枝聚合物（A)、丙烯基条共聚物（B)完全溶解成橡謬 溶液的狀態，以方便泵输送至反應器的作業進行；將前逑 原料溶液分別連纗的餵入第一反應器及/或第二反應器、 及/或其後鑛之反應器中，並配合添加鍵移轉劑及游離劑 、起始劑下進行反應。 當反應混合物被持缠的從第一反應器中取出時，其速 率相當於原料溶液的館料速率，取出之反應混合物再餵入 第二或更多的反應器中進行進一步聚合反應；前述第一或 更多反應器之形式设有待別的限制，但基於接枝共聚物（C )之分散狀態，以及二烯系橡膠之相反轉及其粒徑大小、 分佈之控制等因素，第一反應器以採用完全混合型（CSTR) 反應器為較佳；經前述各反應器之反醮，使其轉化率達到 40〜90重量％為止，最後再將反應後之反應混合物送至脱 揮發装置移除未反應之單匾與溶劑，邸可製得接枝共聚物 (C),其重量平均粒徑在0.3〜10卿之間.以0.8〜為佳。 本發明接枝共聚物（C)之使用量乃相對於100重量份 之苯乙烯系樹脂的2〜60重置份，當前述成份低於2重量 份時，樹脂的耐熱性差，面衝擊強度以及氣體燒痕現象之 第11頁 本紙張尺度適用中國國家揉率（CNS ) A4规格（210X297公釐） ---------装------ΪΤ------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 G r - - A 7 ^ U 〇) 〇 〇 i B7 五、發明説明（C ) 改良效果不足，若大於60重量份，則無法«得高衝擊強度 ，尤其是面衝擊強度性霣。 橡謬接枝共聚物（A)的使用量乃相對於接枝共聚物（C )中單體總合100重量份的0.1〜10重量份，較佳為0.5〜8 重董份，當前述橡睡接枝共聚物（A)的使用量高於10重量 份時，會造成進料溶液黏度過高、溶解分散困難、泵送作 業困難等缺失，而本發明丙烯基条共聚物（B)的使用量乃 相對於接枝共聚物（C)中單鼸總合100重量份的0.1〜10 重量份，較佳為0.5〜8重量份，當前述使用量低於0.1重 量份時，聚合物容易凝聚在一起並沉降於溶液中，而無法 完全被分散溶解於溶液中，造成泵輸送作業困難，反應後 所製得之接枝共聚物（C)會含有粗槠粒.樹脂組成物成品 則會產生魚眼（fish eye)之表面瑕疵，外觀上不佳；若丙 烯基条聚合物（B)之使用量高於10重量份，進料溶液黏度 過高、操作不易，多量之丙烯基条聚合物（B)重覆聚合再 加工也不符經濟效益，當接枝共聚物（C)原料溶液中的橡 謬接枝共聚物（A)及丙烯基条共聚物（B)之使用置皆少於 0.1重量份時，樹脂的面衝擊強度差。 本發明橡膠接枝共聚物（A)之接技率在10〜40¾，而接 枝在橡膠上的硬質共聚物之分子量在4 0,000〜120,00 0時 ，可使組成物得到較佳的衝擊強度與流動性；上述接枝率 傺指接枝於橡謬上之硬質共聚物與橡膠之比值,此硬質 共聚物在本發明為苯乙烯糸單醱、丙烯睛系單體及可共聚 合單體。 第12頁 本紙張尺度速用中國國家搮窣（CNS ) Α4規格（210Χ297公釐） 訂 务 (請先閣讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印製 A7 B7_ 五、發明説明（u ) 本發明之接枝共聚物（D)的製造方法與橡騵接枝共聚 物（A)的製造説明相同，接枝共聚物（D)與橡謬接枝共聚物 (A)可為相同組成，亦可為不同之組成，但基於較佳之衝 擊強度、剛性及流動性間之物性平衡，接枝共聚物（D)之 接枝率在18〜8035之間為佳，其接枝之硬質共聚物的分子 量在40,000〜200,000間為佳，當接枝率低於18ίί或者接 枝之硬質共聚物的分子量低於40,000時，樹脂之衝擊強度 及剛性均不佳，而當接枝率大於80¾、分子畺高於200,000 時，樹脂之流動性差；上述接枝共聚物（D)的使用量乃相 對於苯乙烯条樹脂100重量份的5〜60重量份，當接枝共 聚物（D)之使用量低於5重量份時，樹脂組成物之面衡擊 強度不足，當前述成份高於60重量35時，樹脂的艱燃性及 耐熱性箩差。 本發明之共聚物（E)偽由苯乙烯条單體80〜50重量份 、丙烯精条單腥20〜50重量份，及視需要而選之可共聚合 單體0〜40重量份聚合而得，前述苯乙烯条單鼸、丙烯腈 糸單體及可共聚合單體與橡腰接枝共聚物（A)中之單靂説 明相同，此共聚物（E)可以塊狀、溶液、憨濁、乳化聚合 法製得，其中又以塊狀或溶液聚合法為佳，前述共聚物（E) 之分子量在60,000〜4 00,000之間，尤以80.000〜300,000 間為佳，其使用量乃相對於苯乙烯糸樹脂100重量份的0 〜80重量份。 本發明中所使用之含溴条有機難燃劑均調配於苯乙烯 糸樹脂中，其溴含量宜在40重量以上，尤以55〜85重量 第13頁 本紙張·尺度逋用中國國家標準（CNS ) A4規格（210X 297公釐） ; 訂 (請先閲讀背面之注意事項再填寫本f) 經濟部中央標準局員工消费合作杜印策 Μ Β7____ 五、發明説明（a ) χ為佳，當前述溴含量低於40重量:s時，無法獲得具優異 難燃性之苯乙烯糸樹脂組成物。 本發明中所使用之含溴条有機雞燃劑其具代表性者為 十溴二苯基醚、八溴二苯基_、四溴雯酚A、溴化琿氯型 樹脂、十溴二苯基甲烷、十溴二苯基乙烷、四漠雙酚A — 雙（2,3-二溴丙基_)、四溴雙酚A —雙（烯丙基醚）、苯氧 基在尾端的四溴雙酚A、六溴環十二磺烷、五溴二苯基醚 、2,4,6-三澳册、聚二溴苯基 ® ( poly-dibronophenyl oxide)、雙（三溴苯氣基）乙烷、四溴肽酐、四溴肽酸二 醇_、四溴肽酸酯；雙-溴醛肽亞胺類之Ν,Ν’-(氧-二-對 -次苯基）-雙[3,4,5,6-四溴酞醛亞胺]{^-(<^7-心-?-phenylene )-bis [3 , 4 , 5 , 6-tetrabro-niophtha 1 i m ide] } 、N,Ν’-(次甲基-二-對-次苯基）-雙[3,4,5,6-四溴酞醛亞 胺]{忖，衫’-(116七}1716116-<]卜口-口11611716116)-|515[3,4,5,6-tetfabronioplithaliBiide ]}、Ν,Ν'-(對，間-次苯基）-雙[3 ,4,5,6-四漠社睡亞胺]{1<,1'1’-(?311〇||11-?116时16116)-[3,4 ,5,6-tetrabromophthaliBicle]}、><,((’-(1,2-次乙基）-雙 [3,4,5,6-四溴酞酵亞胺]{N,N，-(l,2-e thy-lene)-bis[3, 4.5.6- 七6七广31)「〇11〇?^11311|«1€|6]}及><,>1'-(1，2-次丁基）- 雯[3,4,5,6-四溴酞醛亞胺]{夂11，-(1,2-1)1^1101^)-“3[ 3.4.5.6- tetrabromophthalinide]}、十漠二苯基丙院、 十溴二苯基丁烷、八溴二苯基丙烷、八溴二苯基丁烷，亦 可使用含氛有機難燃劑，其具代表性者為：1,2,3,4,7,8, 9,10,13,13,14,14-十二氛-1,4,4a,5,6.6a,7,10a,10a,11 第14頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐〉 ---------1------IT------# (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（3) .12,12a-十二氫-1,4,7,10-二甲氣二苯酵（a,e)環辛烯； 其中，較佳之溴糸有機難燃劑為十溴二苯基醚、八溴二苯 基_、四溴雙酚A、溴化環氧樹脂、四溴酞醛亞胺乙烷、 十溴二苯基甲烷及十溴二苯基乙烷；一般含溴糸有機難燃 劑之使用童乃相對於苯乙烯系樹脂100重量份的5〜40重量 份.尤以10〜30重量份為佳；當含溴糸有機化合物之使用 量低於5重量份，雞燃性不充足；當含溴糸有機化合物之 使用量高於40重量份時，樹脂的耐衝擊強度不充足。 本發明為獲得充份的難燃性，可進一步使用難燃助剤 ，例如三氣化二銻、五氧化二銻、三氣化二鐵、硼酸鹽類 、氣氧化鎂、氩氣化鋁等，其中以三氣化二綈為佳，其使 用量相對於100重置份之苯乙烯糸樹脂的1〜30重量份， 較佳為2〜20重量份，更佳為4〜12重量份。 為了更能進一步改良樹脂的衝擊強度，可在本發明中 進一步調配相對於100重量份苯乙烯条樹脂的1〜20重量 份之氛化聚乙烯，較佳為2〜15重量份.當氛化聚乙烯之 使用量不足1重量份時，將使衝擊性缺乏改良的效果，而 經濟部中央榡準局員工消費合作.杜印¾ ---------裝-- (請先閲讀背面之注意事項再填寫本頁) 若使用量超過20重量份時，抗張強度則不佳；前述氣化聚 乙烯以結晶化度0〜45¾、氯含量20〜50重量S；者對樹脂之 衝擊強度而言尤佳。 一般含鹵原子之有機雞燃劑或氱化聚乙烯等在加熱時 ,有產生鹵化氫之傾向，而鹵化氫將促進雞燃性苯乙烯条 樹脂的劣化，並引起明顯的熱變色；為抑制或防止此現象 ，本發明之苯乙烯糸樹脂組成物中通常添加有0.1〜10重 第15頁 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X 297公嫠） 經濟部中央標隼局員工消費合作社印製 A7 B7 五·、發明説明（UL ) 董份的包含金屬皂鹽、金屬氣化物、有機錫化合物等脱鹵 化氫防止劑作為熱安定劑。 又本發明之苯乙烯条樹脂組成物中常須需要添加0.01 〜7重量份的酚条抗翥化剤、硫丙酸酯条抗氣化劑、亞磷 酸酯条抗氧化劑、滑剤及分散劑等。 本發明之樹脂組成物偽調配苯乙烯条樹脂、難燃劑， 並且亦可適量添加用以改良熱可塑性樹脂成形性的光安定 劑、充填劑、著色劑、可塑劑、帶電防止劑及耐候劑等。 為得到本發明之樹脂組成物，其混合方法具代表性者 是以合成樹脂領域中習用之漢歇爾混合機等混合各成份， 乾混後再以諸如押出混合機、捏合機或班伯立混練機等之 混合機熔融混合：以上之混合方法中，使用熔融混練或後 述之成型方法時，若對本發明之樹脂組成物施以高溫作用 ，將引起熱分解或脱鹵化氫反應.故宜於150〜230t之溫 度下實施。 本發明之樹脂組成物在成型時，一般適用射出成型法 、押出成型法、壓縮成型法及中空成型法等之成型方法。 為更進一步詳細説明本發明，再以實施例和物性测試 説明如下，以下組成物之成份除非特別聲明，否則是以佔 全部組成以重量以重量百分計的份數和百分比來表示： <製備例1 >橡膠接枝共聚物（A-1)的製備： ^重鼉松 1 , 3 - 丁 二 烯 150.00 過碕酸评溶液 （U) 15.00 第16頁 本紙張尺度逋用中國國家標準（CNS ) A4规格（210X297公釐） I . 批'^. 訂 各 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印製 Α7 Β7 五、發明说明（lki ) 十二烷基硫酸筘溶液（ίου 20.00 蒸皤水 190.00 乙二醇二甲基丙烯酸酯 0.13 依以上配方在65t反窿溫度下反應12小時，得到轉化 率為94¾ 、固體含董約為40S；、重量平均粒徑0.1卿的合 成橡膠乳液。 另外，以下列成份製造含羧酸基的离分子凝集劑： ^_iiL 重量__份 丙 烯酸乙 酯 90.0 丙 烯 酸 10.0 過硫酸鉀溶液 （U) 0.5 十二烷基硫酸納溶液（10¾) 0.5 蒸蹓水 200.0 依以上配方在75°C反應溫度下反應5小時，得到轉化 率約95¾、pH值6.0的含羧酸基离分子凝集劑。 之後，利用3重量份的含羧酸基高分子凝集劑（乾重） 來肥大100重量份的合成橡謬乳液，所得到的肥大化橡膠 乳液的pH值為8.5,其橡膠粒子之重鼉平均粒徑約為0.31 /ύΠ ◦ 最後，再以前述肥大化橡膠乳液依下逑配方進行接枝 聚合反應，以製造橡謬接枝共聚物（Α-1)。 . 訂 务 (請先閱讀背面之注意事項再填寫本頁) 成 雷 暑 份 肥大化橡謬乳液 (乾重） 100.0 苯 乙 烯 25.0 第17頁 本紙張尺度適用中國國家標窣（CNS ) Α4規格（210Χ 297公釐） 經濟部中央標準局員工消费合作杜印装 A7 _B7_ 五、發明説明（lb) 丙 烯 睛 8.3 第三级一十二烷基硫醇 2.0 異丙苯化過氧化氫 3.0 碕酸亞鐵溶液 （0.2¾) 3.0 甲醛化次碕酸銷溶液（10¾) 0.9 乙二胺四醋酸溶液（0.25S：) 3.0 依上表配方所製得之橡臛接枝共聚物乳液再經脱水、 乾燥至水份含量23；以下，就可製得本發明所需要的橡繆接 枝共聚物（A-1)(橡膠含量75重量X),其橡謬粒子之重量 平均粒徑為0.31娜、接枝率30.5¾.接枝在橡醪上的苯乙 烯一丙烯丨S共聚物的分子量為63,000。 <製備例2>橡膠接枝共聚物（A-2)的製備： 以<製備例1>所製得之合成橡膠乳液（橡膠粒子之 重最平均粒徑〇.1卿），即不經高分子凝集劑之肥大過程， 直接和下表配方進行接枝聚合反窿，以製得橡謬接枝共聚 物（A-2) 〇 ^_ 份 * m_m 合成橡膠乳液（0 1扉）（乾重） 100.0 苯 乙 烯 20.0 丙 烯 I育 8.3 甲 基 丙烯 酸 甲 酯 5.0 第三级 一十二烷基硫醇 2.0 二異丙基苯過氧化氫 3.0 硫酸亞鐵溶液 (0. 2¾) 3.0 第18頁 本紙張尺度遑用中國國家揉準（CNS ) A4规格（210X297公釐） I 訂 备 (請先閲讀背面之注意事項再填寫本f ) 經濟部中央標準局員工消費合作杜印製 Α7 Β7 五、發明説明（！7 ) 甲醛化次碕酸納溶液 （ΙΟϋί) 0.9 乙二胺四醋酸溶液 （0.25Χ) 3.0 製得之橡謬接枝共聚物乳液同<製備例1>之後處理 ,上述橡膠接枝共聚物（Α-2)(橡謬含量75重量X)之重量平 均粒徑為0.1湖，接枝率為26.8¾ ,接枝之苯乙烯一丙嫌 腈一甲基丙烯酸甲酯共聚物的分子量為58,000。 <製備例3>丙烯基糸共聚物（B-1)的製備： 以12 kg/hr的速度將苯乙烯75重量份、丙烯腈18重量 份、甲基丙烯酸甲酯32重量份之原料予以混合，再將乙撑 二硬脂睡胺3.0 g/hr、二苯甲醒過氣化物及第三级—十二 烷基硫醇和後述回收液合併作為館給液，以供給入内溫度 保持在108 t且容積45公升之附有攪拌器的釜型聚合槽中 ，且使反應液中的甲笨比例保持在15 S；，而聚合率保持在 55¾ 〇 當反應液通過脱揮發裝置除去揮發成份後，可得到本 發明所需要的丙烯基条共聚合體的顆粒；另一方面，所除 去之揮發成份以冷凝器凝縮作為回收液，並連續地與前述 原料混合液再使用之；此方法可由二苯甲醛過氣化物的量 調整反應速度，或諝整第三级一十二烷基硫醇之量；最後 以約12kg/hr的速度製成熔融流動指數為1的苯乙烯-丙 烯U寿一甲基丙烯酸甲酯共聚物（B-1)。 <製備例4>丙烯基糸共聚物（B-2)的製備： 直接採用申請人公司所製造之甲基丙烯酸甲酯（商品 名為：ACRYREX CM-205)。 第19頁 本紙張尺度逋用中國國家揉準（CNS ) Μ規格（210X297公釐） ---------餐------ΪΤ------i (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 A7 B7 一- ___ ____ _________ ____ 五、發明説明（s ) <製備例5>接枝共聚物（(:）： 使用7重量份之聚丁二烯（旭化成公司所出品，商品名 --Asadene 55AS)當作二烯条橡膠、0.1重量份之第三-十 二烷基硫醇及0.07重量份之二苯甲醯過氣化物當起始劑， 以及使1.4重量份之搛膠接枝共聚物（A-1)(橡謬含量75重 量％)及1.4重量份的丙烯基糸聚合物（B-1)完全溶解於74.4 重量份的苯乙烯、25.6重量份之丙烯腈及30重量份之乙苯 中，而形成進料溶液；將前述進料溶液連缠送入第一反應 器中，此第一反應器之體横為44公升、反應溫度為lOOt ，其内設置之螺旋式«拌裝置之*拌速度為300 r*f>ia ,於 擻拌装置内設有冷卻循環管，將經過第一反應器反應後之 混合物連續取出並送入第二反應器中，此第二反應器中装 置相同於第一反應器，俟混合物之轉化率達6〇χ時，再将 混合物取出送入脱揮發装置移去未反應之單體及揮發物， 之後將其S出造粒，即可製得橡驂粒子重量平均粒徑為1.1 /a之接枝共聚物（C-1) 〇 依前述製備方法並以附表一所載比例，製造出接枝共 聚物（C-2)、（C-3)、（C-4)、（C-5)、（C-6)。 <製備例6>接枝共聚物（丨)）之製備： 合成橡謬乳液同製備例1 ,但肥大化處理改以3.5重 量份的含羧酸基之高分子凝集劑來肥大100重量份之合成 橡謬乳液，所得到之橡謬乳液之pH值為8.5 ,而且其橡謬 粒子之重量平均粒徑約為0.28卿，並且依下列配方進行接 枝聚合反應，以得到接枝共聚物（D)。 第20頁 本紙張尺度逋用中國國家揉準（CNS ) A4規格（210X297公釐） .T 各 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印装 A7 B7 五、發明说明（θ) ^_iit 重曇 肥大化橡膠乳液 (乾重） 100. 苯 乙 烯 40. 丙 烯 睛 13. 第三级一十二烷基硫醇 2.0 異丙苯化過氧化氫 3.0 硫酸亞鐵溶液 （0.230 3.0 甲醛化次硫酸納溶液 （10X) 0.9 乙二胺四醋酸溶液 （0.253!) 3.0 上述接枝共聚物（D)(橡驩含量65重量《)之重量平均粒 徑為0.28厲，接枝率為42 X,接枝之苯乙烯-丙烯睛共聚 物的分子量為80,000。 <製備例7>共聚物（E)的製備： 以12 kg/hr的速度將苯乙烯76重量份、丙烯腈24重量 份之原料予以混合，再將乙撑二硬脂醯胺3.0 g/hr、二苯 甲醯過氣化物、第三级-十二烷基硫醇，以及後述反應所 除去之揮發份經冷凝後所形成之回收液合併作為餵給液， 同製備例3之聚合程序得到熔融流動指數1.2之苯乙嫌 一丙烯腈共聚物（E)。 下述實施例和比較例所潮得的物性和成型外觀的測試 標準如下： 来面衝擊強度：依ASTM D-3763規定测試，單位以kg.cn 表示。 来雞燃性試驗：依據美規UL-94垂直燃燒試驗（厚度1/16英 第21頁 本紙張尺度適用中國國家橾準（CNS ) Α4規格（210X297公釐） ---------f------ΐτ------# (請先閲讀背面之注意事項再填寫本頁) 經濟部中央橾隼局員工消費合作杜印製 A7 B7 ------- 五、發明説明（π) 吋）法實施，Ο表試通過試驗，X表示未通遇潮試。 *耐熱性試驗：依美規ASTMD-1525 規定測試。 *抗氣體燒痕試驗：在固定條件下，射出成型時棋具採Pin gate模具，料茼溫度設定在250Ό,覼察所得之成型品 產生氣體燒痕之慵況，咐表二中之符號意義為：〇表示 無氣髏燒痕，X則表示氣體燒痕嚴重。 来成品外觀：成型品之試驗Η以目視檢測，外觀平整者以 〇表示，表面有粒狀凸起或魚眼者以X表示。 富旃例 <實施例1 > 將附表一所製得之接枝共聚物（C-1) 30重量份、接枝 共聚物（D) 25重量份、共聚物（Ε) 45重量份，以及溴含量 59¾之澳化環氣型樹脂難燃劑（日本DIC公司產品，商品名 為EC-14U6.4重量、三氧化二鏵（Sba〇3)8重量份、氛化聚 乙烯10重量份，以漢敢爾混合機乾混，再以料筒溫度設定 在205、模頭溫度設定在220C之附排氣口的二轅押出機 製得粒狀的難燃性苯乙烯条樹脂.並進行各項物性測試， 测得的結果載於附表二。 <實施例2 > 同實施例1之操作條件.並以附表二之配方押出、製 粒，並成型測試用試Μ.测得之物性亦載於附表二。 <實施例3〉 同實施例1之操作條件，但以溴含量59«之四溴雙酚 第22頁 本紙張尺度適用中國國家揉準（CNS ) Α4规格（210X297公釐） ---------裝------訂 線 (請先閱讀背面之注意事項再填寫本頁) Α7 Β7 Ο. 五 '發明説明（二丨） A雞燃劑（GREAT LAKES公司產品.商品名為BA-59P)取代 實施例1之澳化環氧型樹脂，並以附表二之配方押出、製 粒且進行各項物性試驗，测得之物性亦載於附表二。 <實施例4 > 同實施例1之操作條件，但以溴含量59¾之四溴雙酚 A難燃劑（GREAT LAKES公司產品.商品名為BA-59P)取代 簧施例1之溴化環氣型樹脂，並以附表二之配方押出、製 粒且進行各項物性試驗，測得之物性亦載於附表二。 <實施例5 > 同實施例1之操作條件，並以附表二之配方押出、製 粒，並成型测試用試M,測得之物性亦載於附表二。 <實施例6 > 同實施例1之操作條件，但難燃劑以溴含量59¾之溴 化環氣型樹脂及十漠二苯基SMDeca brorao diphenyl oxide, 簡稱 Deca ) 兩者併用 ，成品再進行各項物性試驗 ， 測得之物性亦載於附表二。 〈比較例1 > 同實施例1之操作條件，但不加入接枝共聚物（C), 製得之成品同樣進行各項物性測試，結果亦載於附表二。 <比較例2 > 同實施例1之操作磔件，但接枝共聚物（C)中不添加 丙烯基糸共聚物（B),所成型之澜試Η亦測其物性，並載 於附表二中。 <比較例3 > 第23頁 本紙張尺度遑用中國國家橾準（CNS ) Α4規格（210X297公簸） ---------装------訂 線 (請先閲讀背面之注意事項再填寫本瓦) 經濟部中夬標隼局員工消費合作杜印製 經濟部中央樣隼扃員工消費合作社印製 A7 B7__ 五、發明説明（& ) 同實施例1之操作條件，但接枝共聚物（C)中不添加 橡膠接枝共聚物（A)及丙烯基条共聚物（B),裂得之成品 同樣進行各項物性測試，结果亦載於附表二。 <比較例4 > 同實施例1之操作條件，但不加入接枝共聚物（D), 製得之成品同樣進行各項物性測試，結果亦載於附表二。 <比較例5 > 同實施例1之操作條件，但雞燃劑之添加置低於5重 量份，所製得之成品同樣進行各項物性測試，結果亦載於 附表二。 <比較例6 > 同實施例1之操作條件，但添加之接枝共聚物（C)過 置，製得之成品同樣進行各項物性測試，結果亦載於附表 —-〇 由比較例1之試驗結果可知，本發明樹脂組成中若不 添加接枝共聚物（C).不僅樹脂之耐熱性及面衝擊強度不 佳，成型品之氣體燒痕也蔌重，由比較例2之测試結果顥 示，當接枝共聚物（C)中不含丙烯基条共聚物（B),成型 品的外觀不良，而當接枝共聚物（C)中未添加橡膠接枝共 聚物（A)及丙烯基条共聚物（B)時，樹脂之面衝擊強度不佳 ，此由比較例3之測試結果可知；再當樹脂組成物中缺少 接枝共聚物（D)時，樹脂之面衝擊強度明顯不足，此由比 較例4之試驗結果可證明；而由比較例5之試驗結果顯示 ，當樹脂組成物中的雞燃劑用量不足時，其難燃性無法通 第24頁 本紙張尺度遴用中國國家揉準（CNS ) A4規格（210X29*7公釐） ---------^.------1T------0 (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（β) 過試驗，而當接枝共聚物（C)之添加董超過60重量S：時， 刖會造成面衝擊強度不佳的現象，此由比較例6的試驗結 果可證明。 再觀贾施例1〜6,本發明經前述各成份及使用量之 限制，確實可使樹脂具有良好之難燃性、高耐熱性，並同 時具有優異的面衝擊強度、抗氣體燒痕及成型品外觀優良 等性質，俾使難燃性苯乙烯集樹脂組成物在物性上更臻完 善，而可供產業上利用，爰依法提出發明專利之申請。 惟以上所述僅為本發明數較佳可行實施例，舉凡熟悉 此項技苞人仕，其依本發明精神範矚所做之修飾或變更， 均理應包念在本案申請專利範圔内。 附表一：本發明之實施例與比較例所使用接枝共聚物（C) 之組合成份及使用量。 附表二：本發明之實施例與比較例之成份、各成份的使用 置，以及物性試驗結果。 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消费合作杜印震 第25頁 本紙張尺度適用中國國家標準（CNS ) A#規格（21〇χ297公釐）Employee's consumer cooperation du printing suit of the Central Bureau of Standards of the Ministry of Economic Affairs ^ ^ 6 u 1 A7 _B7__ V. Description of the invention (丨) The present invention has a good flame retardancy, high heat resistance, and has ® out-of-plane impact strength, A chicken flammable styrene strip resin composition with properties such as resistance to gas burrs and excellent appearance of molded products. Styrene resin has been widely used in daily life, especially in household appliances and commercial machinery, such as the shell of recorders, televisions, computers, typewriters, etc., which are mostly made of styrene strip resin . Although these resin products have the advantages of low price, light weight, and good mechanical strength, but compared with metal, the disadvantage is that the resin is flammable. Therefore, in some fire accidents, there is no lack of flammability due to resin products For example, it is the most important issue in resin industry technology. Generally speaking, there are two ways to make the resin products incombustible. The first is to mix the reactive chicken flammable substances and the reactive monomers in the resin and carry out the polymerization reaction together to give the final resin product chicken combustion. This method is more commonly used on thermosetting resins. Another method is to mix and mix non-reactive flame-retardant substances and resins with a mixing device such as an extruder, so that the resin has Chicken burning, this method is more commonly used in thermoplastic resin. In order to impart flammability to the styrene resin, the commonly used flame retardant in the conventional technology is generally an organic chicken flame retardant containing window element, especially an organic flame retardant containing atmosphere or bromine, such as ten Bromodiphenyl »(and 031) 1'〇111〇 (^ 口 -heny 1 〇xi de), octa-diphenyl ether (〇c tabromod i pheny 1 ox i de), tetrahydrobis SSA (tetrabromobisphenyl A ), Bis (dihydrobenzene gas) yiyuan [bis (t "ibronophenoxy) ethane], 1,2- bis (four Australian soft acetylene) Page 03 This paper scale is applicable to China National Standard (CNS) A4 specifications (210X297 Cli) --------- 装 ------ ΪΤ ------ # (Please read the precautions on the back before filling this page) Employee consumption cooperation du printing by the Central Standards Bureau of the Ministry of Economic Affairs Q-rc ', f A / 〇〇〇〇〇__ _b7__ Fifth, the description of the invention (two) imino group) Yiyuan [ethylene bis (tetrab "〇B〇phthalinide)], double (six« Chen Ping two: Suspicion) Zhuoxinyuan [bis (hexachlor〇-cyclopent-adiene) cyclooctane], Shiaodiphenylmethyl courtyard, decamodiphenylethane, etc .; some flame retardants are usually used with an appropriate proportion of inorganic Combustion aid to reduce The amount of halogen-containing organic compounds used to avoid the addition of halogen-containing organic compounds reduces the physical properties of raw materials such as mechanical properties and heat resistance of styrene strip resins. On the other hand, the addition of flame retardants to styrene resins The impact on raw materials is based on the impact strength and the formation of burn marks (Gas bU "nning) on the surface of the molded product during injection molding. It is the most important thing for the home appliance industry, business machinery, and electronic information industry. When the impact strength of the resin is insufficient It will cause the molded product to be unable to withstand the collision during the transportation and installation due to the gap-like mesh structure (heat dissipation design), and even cause cracks and damage to the soil. In addition, the resin and flame retardant are easy to crack during resin injection molding , And produce decomposable acidic substances, such as bromic acid (HBr), hydrochloric acid (HCI), etc .; especially for the pin gate molds that are often used recently, because the caliber of the filling mouth is reduced, it is easy to produce greater frictional heat, so At the time of injection, the increase in the temperature of the resin itself will make the resin cracking more heavy, which will also cause a large amount of gas generation; the volatile components generated above Dissolved substances (ie, the aforementioned bromic acid, hydrazonic acid, etc.) will produce gas burn marks on the surface of the molded product after cooling, which will also affect the appearance of the finished product. The aforementioned deficiency will make the use of the resin greatly restricted. For example .In the case of US Patent No. 3830766, it is mentioned that the use of tetrabromobisphenol A as a flame retardant, and the combination of flame retardant resin composition with triflame antimony, tri-polyethylene and other flame retardant additives can be improved. Resin ductility and anti-aging page 04 The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Order (please read the precautions on the back before filling out this page) Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative A7 B7_ V. Description of the invention (3) Chemical properties, but when tetrabromobisphenol A is added to the styrene strip resin, it will obviously accumulate the physical properties of the raw materials, such as heat resistance, surface impact strength, etc., and Even if the injection molded product has gas burn marks, it cannot be changed, so it is restricted in use. In order to improve the aforementioned deficiencies, the inventors of this case have found through research that blending halogen-containing organic flame retardants in the styrene resin to be determined can broadcast good flame retardancy and heat resistance, impact strength, appearance and gas resistance of the resin surface A non-flammable styrene resin composition with burn marks. Love is, the main purpose of the present invention is to provide a flame-retardant styrene strip resin composition having good flame retardancy, heat resistance, and excellent surface impact strength, appearance, and gas burn resistance. However, the flame-retardant styrene resin composition of the present invention mainly includes: (1) 100 parts by weight of styrene strip resin, the pseudo-response is: (1) The rubber with a weight average particle diameter of 0.05 ~ 0.8 Branch copolymer (A) 0.1 to 10 parts by weight, diene shit rubber 2 to 25 parts by weight and propylene-based bar copolymer (B) 0.1 to 10 parts by weight, with the following monomers based on a total of 100 parts by weight : 80 to 45 parts by weight of styrene strip monomer, 15 to 50 parts by weight of acrylonitrile strip monomer, and copolymerizable monomers of 0 to 40 parts by weight to obtain block-shaped and / or solution-polymerized graft copolymers (C ) 2 ~ 60 parts by weight; (2) In the presence of 50 ~ 85 parts by weight of rubber emulsion with a weight average particle size of 0.05 ~ 0.8_, it can be mixed with styrene-based single alligator, acrylic eye strips, and as needed Polymerization unit «mixture 50 ~ 15 parts by weight of graft copolymer obtained by emulsified graft polymerization (D) 5 ~ 60 reset parts; page 05 This paper size is applicable to China National Standard (CNS) A4 specification (21〇X297 Mm) --------- approved clothing ----- 1T ------ ^ (please read the precautions on the back before filling out this page) Staff of Central Bureau of Standards, Ministry of Economic Affairs Printed by the Fee Cooperative Society J__B7___ V. Description of the invention (4 ·) (3) 80 to 50 parts by weight of styrene strip monomer, 20 to 50 parts by weight of acrylonitrile monomer and polymerization of copolymerizable monomers as required ~ 40 parts by weight of the copolymer obtained by polymerization (E) 0 ~ 80 parts by weight; (2) 5 ~ 40 parts by weight of bromine content 40 parts by weight S! The above-mentioned bromine-containing organic flame retardant. According to the foregoing composition, Di can produce a flame-retardant styrene strip resin composition that has both good flame retardancy, high heat resistance, excellent surface impact strength, resistance to gas burns, and excellent appearance of molded products. The rubber graft copolymer (A) of the present invention is prepared by emulsification polymerization, and the preferred manufacturing method is to pseudopolymerize diene strips and other copolymerizable monolep directly to the reset average particle size of 0.05 by emulsion polymerization ~ 0.8% of the rubber emulsion, the above monomers can also be made into a small particle size rubber emulsion of 0.05 ~ 0.2 by the emulsion polymerization method, and then the frozen small size method, mechanical enlargement method, or additive enlargement method to reduce the small particle size The rubber emulsion emulsion is enlarged into 0.15 ~ 0.8 Qingzhi's rubber emulsion; the additives used in the additive hypertrophy method can be: acidic substances such as acetic anhydride, hydrogen chloride, sulfuric acid, or sodium oxychloride, potassium oxychloride, calcium oxychloride, etc. Basic substances, and (meth) acrylic strip- (meth) acrylic acid_strip copolymers (such as methacrylic acid-butyl acrylate copolymer, methacrylic acid-ethyl acrylate copolymer), etc. Polymer coagulant. Add 50 ~ 85 parts by weight of styrene strip monomers, 50 ~ 15 parts by weight of propylene nitrile, and other copolymerizable monomers of 0 ~ 30 parts by weight, and appropriate emulsifying agent and initiator Carry out graft polymerization; the above initiators can use common technical initiators, for example: di benzoyl peroxide (di benzoyl peroxide), diisopropyl benzene hydrogen peroxide (diisop- page 06 of this paper Standards apply to China National Standards (CNS) A4 (210X297mm) --------- ^ ------ ΪΤ ------ # (Please read the notes on the back before filling in This page) The Ministry of Economic Affairs, Central Bureau of Standards, Employee and Consumer Cooperatives printed 11 A7 B7 Five 'invention description (s) ropyl benzene hydroperoxide), tert-butyl hydroperoxide, cumene cumene cumene peroxide (cumene hydroperoxide), potassium persulfate (potassiumpersu 1 fate), etc. Among them, organic pergasified hydrogen is preferred. The graft copolymer (A) of the present invention can use an activator of a gasification reduction catalyst system in the polymerization fashion, or an activator of conventional technology such as iron ion, such as sodium pyrophosphate dextrose), sodium dioxetite (sodiu π for in a 1 dehydesu 1 foxy 1 ate), ascorbic acid, dihydroxy ace-tone, etc., in addition. Ethylenediamine tetraacetate (eth-y 1 enedia B netetr * aceticacidsa 11) can be added to promote its effect; and the source of iron ions can use iron cyanide or ferrous lanate. The graft ratio of the aforementioned rubber graft copolymer (A) can be controlled by the polymerization reaction conditions, for example: the polymerization temperature, the initial two, the amount and type of emulsifier, chain transfer agent, the method of adding single snakehead, etc. Control; can also add bond transfer agent according to the conventional technology to adjust the molecular weight of the graft copolymer (A). Common transfer agents are: n-butyl nercaptan, n-octyl Thiol (n-octy 丨 nercaptan), n-h decyl thiol (n-dodecyl uercaptan), third-h dioctyl thiol (te "t-do-decyl mercaptan); the above rubber The molecular weight of the waist graft copolymer (A) can also be adjusted by changing the polymerization conditions such as the polymerization temperature, the type and amount of the initiator, and the method of adding the monomer. The reaction temperature of the graft polymerization is below 90Ό, especially It is better to be between 30 ~ 80T; the monomers for grafting can be added at one time, or can be added in batches, or can be added continuously or the various monomers should be grafted together. Page 07 (CMS) A4 specification (210X297mm) (please read the notes on the back before filling in this page), vs economy A7 B7 is printed by the Employees ’Cooperative of the Central Standards Bureau of the Ministry of Education. 5. Description of the invention (t). In this way, the rubber graft copolymer emulsion can be obtained; Obtaining the graft copolymer (A) of fine mash with a weight average particle diameter of 0.05 to 0.8 required by the present invention < Although the graft copolymer (A) of the present invention can be prepared by various methods mentioned above, it is better to use the rubber emulsion of the hypertrophy method based on the principle of shortening the polymerization time of the rubber emulsion to improve the manufacturing efficiency. Among them, for the purpose of increasing the uniformity of the particle size and reducing the agglomeration, it is better to add a carboxylate group-containing polymer coagulant to enlarge the rubber emulsion. The styrene strip monomer used in the rubber graft copolymer (A) of the present invention may be styrene, α-methylstyrene, α- «styrene, pt-butylstyrene, P-methylstyrene , 〇-cyanostyrene, P-chlorostyrene, 2,5-di-distyrene, 3,4-di-tristyrene, 2, 4, 6-tribromostyrene, 2.5-dibromostyrene Among others, styrene or α-methylstyrene is preferred. The acrylonitrile strip monomers used may be: acrylonitrile, ct-methacrylic acid, etc .; among them, acrylonitrile is preferred. The copolymerizable monomers used in the rubber graft copolymer (A) of the present invention may be (meth) acrylate ester monohydrate, malealdimine, etc .; wherein (meth) acrylate Shito can be: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, Dodecyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, dimethylcyanoethyl methacrylate, etc., among which methyl methacrylate is preferred. Page 08 This paper scale is applicable to the Chinese National Standard (CMS) Α4 specification (210 X 297 mm) --------- ^ ------ ΐτ ------ # (Please read first (Notes on the back and then fill out this page) A7 B7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (up) The maleimide strips can be: maleimide, N-methyl horse Maleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, octylmaleimide, N-dodecylmaleimide Acetamide, N-Chenhexylmaleimide, N-phenylmaleimide, N-2,3-tolylmaleimide, N-2,4-tolylmaleimide Amine, N-2,3-ethylphenylmaleimide, N-2,4-ethylbenzylmaleimide, N-2,3-butylphenylmaleimide, N-2 , 4-butylphenylmaleimide, N-2,6-tolylmaleimide, N-2,3-aminophenylmalealdimine, N-2.4-phenylphenylmaleimide Aldimine, N-2,3-bromophenylmaleimide, N-2,4-bromophenylmaleimide, etc., among which N-methylmaleimide is the best . The propylene-based copolymer (B) of the present invention is selected from: (meth) acrylic acid ester monomers and acrylonitrile ribbon monomers, at least one type of monomers 10 to 100% by weight, and styrene ribbon monomers 0 to 80 weight, and other copolymerizable monomers 0 ~ 30 weight χ; the types of monomers in the above components are approximately the same as those contained in the rubber graft copolymer (Α), the difference is that: propylene-based copolymerization The other copolymerizable monomers in substance (B) do not contain maleimide strip monomers; the polymerization method can be obtained by various polymerization methods such as solution, block, emulsion or suspension, etc. Polymerization method is preferred. The diene Shito rubber used in the graft copolymer (C) of the present invention is: after the ion polymerization of the diene Shi monomer component, the glass transition temperature is -2〇t: the following polymerization certificate, preferably diene rubber For example: butadiene rubber, isoprene rubber mash, cyanobutadiene rubber, etc .; among them, butadiene rubber has high cis (Hi-Cis) content and low cis (Lovj-Cis) content. ; The typical weight composition of cis (Cis) / vinyl (Vinyl) in high-cis rubber is 94 ~ 98. Page 09 This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297mm)- -------- ^ ------ ir ------ line. (Please read the precautions on the back before filling out this page) Employee consumption cooperation of the Central Standard Falcon Bureau of the Ministry of Economic Affairs Du Printed A7 B7 Fifth, the description of the invention (s)% / 1 ~ 5%, the rest of the composition is a trans (Trans) structure; its Mooney viscosity is between 20 ~ 120, and the molecular home model is 100, 000 ~ 800,000. Good; in the low cis oak, the typical weight composition of cis / vinyl is in the range of 20 ~ 40% / 1 ~ 20%, the rest is in the trans structure, and its Mooney viscosity is between 20 ~ 120, other suitable rubber materials Still have Absurd acrylonitrile rubber, styrene / butadiene rubber, or a mixture of different rubbers above; dumb ethylene / butadiene rubber, commonly known as S B R. Di The styrene / butadiene copolymerized rubber mash suitable for the present invention can be a di-block copolymer, a tri-block copolymer, or a random copolymer. Or star type copolymerization (star type). The weight ratio range of styrene / butadiene rubber is preferably from 5/100 to 80/20, and the molecular weight range is preferably from 50,000 to 600,000. The above-mentioned rubbers suitable for the present invention are butadiene rubber and styrene / butadiene Rubber is better. Among them, butadiene rubber is better. The graft copolymer (C) of the present invention is a pseudo rubber graft copolymer (A) 0.1 to 10 parts by weight, a diene rubber rubber 2 to 25 parts by weight, and a propylene-based copolymer (B) 0.1 to 10. Parts by weight, and the following single snakeheads totaling 100 replacement parts: styrene-based monobranched 80 ~ 45 5 parts by weight, acrylonitrile-based monomer 15 ~ 50 parts by weight and copolymerizable monomer 0 ~ 40 parts by weight , Obtained by polymerization in bulk and / or solution polymerization. In detail, the present invention presumably mixes and dissolves the above-mentioned single-component grafted polymer (A), diene rubber, propylene-based copolymer (B), and a solvent selected as needed to form a raw material solution. Send into the reactor for polymerization; or mix and dissolve part of the aforementioned monofilaments, rubber yam graft polymer (A), propylene-based copolymer (B), and the solvent selected as required to form an independent raw material. The size of the page paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) --------- 1 ------ IT ------ # (Please read the notes on the back first (Fill in this page again) Du Yin, Staff Consumption Cooperation, Central Bureau of Standards, Ministry of Economic Affairs A7 B7 V. Description of invention (7) Liquid, and then dissolve the remaining monomers with diene shrub rubber to form another raw material solution. The two raw material solutions are Feed into the reactor for polymerization. The aforementioned raw material mixture can be dissolved in a traditional dissolving tank with high shear stress and high stirring speed. This dissolving tank can be used: with a band-shaped vortex S mixing leaf, a propeller-type pseudo-mixing propeller, or other can produce high shear Stress «leaf mixing, etc., can dissolve the above-mentioned diene Shitou rubber or graft copolymer (A), propylene-based copolymer (B) completely into a rubbery solution in a sufficient time to facilitate The operation of pumping to the reactor is carried out; feed the raw material solution into the first reactor and / or the second reactor, and / or the reactor behind the mine successively, together with adding the key transfer agent With free agent and initiator. When the reaction mixture is entangled and taken out from the first reactor, its rate is equivalent to the material rate of the raw material solution, and the taken out reaction mixture is fed into the second or more reactors for further polymerization; The form of one or more reactors is subject to other restrictions, but based on the dispersion state of the graft copolymer (C) and the reversal of the diene rubber and the control of its particle size and distribution, the first reaction The reactor is preferably a fully mixed (CSTR) reactor; after the reaction of the above reactors, the conversion rate reaches 40 ~ 90% by weight, and finally the reaction mixture after the reaction is sent to the devolatilization device to move Except for the unreacted single plaque and solvent, Di can prepare the graft copolymer (C), whose weight average particle size is between 0.3 ~ 10%. 0.8 ~ is preferred. The amount of the graft copolymer (C) used in the present invention is 2 to 60 parts by weight relative to 100 parts by weight of the styrene resin. When the aforementioned components are less than 2 parts by weight, the resin has poor heat resistance, surface impact strength and Gas burn marks on the 11th page of this paper scale is applicable to China's national rubbing rate (CNS) A4 specification (210X297 mm) --------- installed ------ ΪΤ ------ ^ (Please read the precautions on the back before filling this page) Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative G r--A 7 ^ U 〇) 〇〇i B7 V. Invention description (C) The improvement effect is insufficient, if it is greater than With 60 parts by weight, high impact strength, especially surface impact strength, cannot be achieved. The amount of the rubber graft copolymer (A) used is 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight relative to 100 parts by weight of the total monomers in the graft copolymer (C). When the amount of the sleeping graft copolymer (A) is higher than 10 parts by weight, it will cause the lack of viscosity of the feed solution, the difficulty of dissolution and dispersion, and the difficulty of pumping operations. However, the propylene-based copolymer (B) of the present invention The amount used is 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, relative to 100 parts by weight of the total amount of monomers in the graft copolymer (C). When the aforementioned amount is less than 0.1 parts by weight, the polymer is easy Coagulates together and settles in the solution, but cannot be completely dispersed and dissolved in the solution, which makes the pumping operation difficult. The graft copolymer (C) prepared after the reaction will contain coarse granules. The finished resin composition will be The surface defects of fish eyes are produced, and the appearance is not good; if the amount of propylene-based polymer (B) is higher than 10 parts by weight, the viscosity of the feed solution is too high, the operation is not easy, and a large amount of propylene-based bars are polymerized (B) Repeated polymerization and reprocessing are not economical. When the graft copolymer ( C) When both the rubber graft copolymer (A) and the propylene-based copolymer (B) in the raw material solution are used at less than 0.1 parts by weight, the surface impact strength of the resin is poor. The grafting rate of the rubber graft copolymer (A) of the present invention is from 10 to 40¾, and when the molecular weight of the hard copolymer grafted on the rubber is from 40,000 to 120,000, the composition can get better impact Strength and fluidity; the above-mentioned graft ratio ye refers to the ratio of hard copolymer and rubber grafted on rubber, this hard copolymer is styrene-based monomers, acrylic monomers and copolymerizable monomers in the present invention body. Page 12 The size of this paper is quickly used in China National Standard (CNS) Α4 specification (210Χ297mm) Ordering (please read the precautions on the back first and then fill out this page) Printed by the Ministry of Economic Affairs Central Standard Falcon Bureau Staff Consumer Cooperative A7 B7_ V. Description of the invention (u) The manufacturing method of the graft copolymer (D) of the present invention is the same as that of the rubber graft copolymer (A). The graft copolymer (D) and the rubber graft copolymer (A) may be the same composition or different compositions, but based on better physical balance between impact strength, rigidity and fluidity, the grafting ratio of the graft copolymer (D) is preferably between 18 and 8035 The molecular weight of the grafted hard copolymer is preferably between 40,000 and 200,000. When the grafting rate is less than 18L or the molecular weight of the grafted hard copolymer is less than 40,000, the impact strength and rigidity of the resin are not good, and When the grafting ratio is greater than 80¾ and the molecular weight is higher than 200,000, the flowability of the resin is poor; the amount of the graft copolymer (D) used is 5 to 60 parts by weight relative to 100 parts by weight of the styrene strip resin. When the amount of copolymer (D) used is less than 5 parts by weight, The surface impact strength of the resin composition is insufficient. When the aforementioned components are higher than 60 and 35 by weight, the flame retardancy and heat resistance of the resin are poor. The copolymer (E) of the present invention is formed by polymerizing 80 to 50 parts by weight of styrene strip monomers, 20 to 50 parts by weight of propylene fine strips, and optionally 0 to 40 parts by weight of copolymerizable monomers. It can be obtained that the foregoing styrene strip monomers, acrylonitrile and monomers and copolymerizable monomers have the same description as the single bolt in the rubber waist graft copolymer (A). This copolymer (E) can be in the form of blocks, solutions, It is prepared by turbidity and emulsification polymerization method, which is preferably block or solution polymerization method. The molecular weight of the aforementioned copolymer (E) is between 60,000 and 40,000, especially between 80.000 and 300,000, and its usage is relative to 0 to 80 parts by weight of 100 parts by weight of styrene resin. The bromine-containing organic flame retardants used in the present invention are all formulated in styrene resin, and the bromine content should be more than 40 weights, especially 55 to 85 weights. CNS) A4 specification (210X 297mm); Order (please read the notes on the back before filling in this f) Employee Consumer Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du Yince Μ Β7 ____ V. Invention description (a) χ is better, when When the aforementioned bromine content is less than 40 weight: s, a styrene-tooth resin composition with excellent flame retardancy cannot be obtained. The representative bromine-containing organic chicken burning agents used in the present invention are decabromodiphenyl ether, octabromodiphenyl _, tetrabromobenzyl A, brominated chlorinated resin, decabromodiphenyl Methane, decabromodiphenylethane, tetrabromobisphenol A — bis (2,3-dibromopropyl_), tetrabromobisphenol A — bis (allyl ether), phenoxy at the end Tetrabromobisphenol A, hexabromocyclododecane, pentabromodiphenyl ether, 2,4,6-Tri-Alumina, poly-dibronophenyl oxide, bis (tribromobenzene gas Group) ethane, tetrabromopeptide anhydride, tetrabromopeptide diol_, tetrabromopeptide ester; bis-bromoaldehyde peptide imines of N, Ν '-(oxy-di-p-phenylene)- Bis [3,4,5,6-tetrabromophthalaldehydeimine] {^-( < ^ 7- 心-?-phenylene) -bis [3, 4, 5, 6-tetrabro-niophtha 1 im ide]}, N, Ν '-(methine-di-p-phenylene)- Bis [3,4,5,6-Tetrabromophthalaldehydeimine] {忖 ， 衣 '-(116 七} 1716116- <] Bukou- 口 11611716116)-| 515 [3,4,5,6-tetfabronioplithaliBiide]}, Ν, Ν '-(p-, m-phenylene) -bis [3, 4,5,6- Simoshe sleeping imine] {1 <, 1'1 ’-(? 311〇 || 11-? 116 时 16116)-[3,4, 5,6-tetrabromophthaliBicle]}, > <, (('-(1,2-ethylidene) -bis [3,4,5,6-tetrabromophthalimide] {N, N ，-(l, 2-e thy-lene) -bis [3, 4.5.6- 七 6 七 广 31) "〇11〇? ^ 11311 |« 1 € | 6]} &> <, > 1 '-(1,2-Benzyl) -wen [3,4,5,6-tetrabromophthalaldehydeimine] {夂 11,-(1,2-1) 1 ^ 1101 ^)-"3 [3.4.5.6- tetrabromophthalinide]}, decabromodiphenylpropionate, decabromodiphenylbutane, octabromodiphenylpropane, octabromodiphenylbutane, and also containing atmosphere Organic flame retardants, the representative ones are: 1,2,3,4,7,8, 9,10,13,13,14,14-dodecane-1,4,4a, 5,6.6a , 7,10a, 10a, 11 Page 14 This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297mm> --------- 1 ------ IT ---- -# (Please read the precautions on the back before filling in this page) A7 B7 V. Description of the invention (3) .12,12a-dodecane-1,4,7,10-Dimethyl gas diphenyl yeast (a , e) Cycloctene; Among them, the preferred bromine-based organic flame retardants are decabromodiphenyl ether, octabromodiphenyl, tetrabromobisphenol A, brominated epoxy resin, and tetrabromophthalimide. Ethane, decabromodiphenylmethane and decabromodiphenylethane; the use of organic flame retardants containing bromine is generally 5 ~ 40 parts by weight relative to 100 parts by weight of styrene resin. Especially 10 ~ 30 parts by weight is better; when the amount of organic compounds containing bromine is less than 5 parts by weight , The chicken's flammability is not sufficient; when the amount of bromine-containing organic compounds used is higher than 40 parts by weight, the impact resistance of the resin is not sufficient. In order to obtain sufficient flame retardancy, the invention can further use flame retardant additives, For example, tri-gasified antimony, antimony pentoxide, tri-ferrous iron, borate, magnesium oxide, argon vaporized aluminum, etc., among which tri-gasified ditantium is better, its usage is reset to 100 1 to 30 parts by weight of styrene resin, preferably 2 to 20 parts by weight, more preferably 4 to 12 parts by weight. In order to further improve the impact strength of the resin, it can be further formulated in the present invention relative to 100 parts by weight of styrene strip resin, 1 ~ 20 parts by weight of atmospheric polyethylene, preferably 2 ~ 15 parts by weight. When the amount of atmospheric polyethylene is less than 1 part by weight, the impact will lack improvement effect , And the consumption cooperation of the Central Bureau of Economics of the Ministry of Economic Affairs. Du Yin ¾ --------- Install-(please read the precautions on the back before filling in this page). If the amount used exceeds 20 parts by weight, resist The tensile strength is not good; the aforementioned gasified polyethylene has a crystallinity of 0 ~ 45¾ and a chlorine content of 20 ~ 50 The amount S; the impact strength of the resin is particularly good. Generally, organic halogen burning agent containing halogen atoms or tritized polyethylene, etc., tend to produce hydrogen halide when heated, and hydrogen halide will promote chicken burning styrene The degradation of the resin and cause obvious thermal discoloration; in order to suppress or prevent this phenomenon, the styrene resin composition of the present invention is usually added with 0.1 ~ 10 weights. Page 15 This paper standard is applicable to China National Standard (CNS) A4 specification (210X 297 gong) A7 B7 printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economy V. Invention Description (UL) The director ’s dehydrohalogenation inhibitor containing metal soap salts, metal vapors, organic tin compounds, etc. As a heat stabilizer. In addition, in the styrene strip resin composition of the present invention, it is often necessary to add 0.01 to 7 parts by weight of a phenol strip anti-chemical agent, a thiopropionate strip anti-gasification agent, a phosphite strip antioxidant, a slip agent, and a dispersant. The resin composition of the present invention is pseudo-blended with styrene strip resin and flame retardant, and light stabilizers, fillers, colorants, plasticizers, electrification inhibitors and weathering agents for improving the moldability of thermoplastic resins can also be added in appropriate amounts Wait. In order to obtain the resin composition of the present invention, a typical mixing method is to mix the components with a Hanscher mixer conventionally used in the field of synthetic resins, and then dry-mix it with an extruder mixer, kneader, or Banbury, for example. Melt mixing of a mixer such as a kneading machine: In the above mixing method, when melt kneading or the molding method described later is used, if a high temperature effect is applied to the resin composition of the present invention, it will cause thermal decomposition or dehydrohalogenation reaction. Implemented at a temperature of 150 ~ 230t. When molding the resin composition of the present invention, injection molding methods, extrusion molding methods, compression molding methods, hollow molding methods, and other molding methods are generally applied. In order to explain the present invention in further detail, the following examples and physical property tests are described below. Unless otherwise stated, the ingredients of the following compositions are expressed in parts and percentages by weight percent of the total composition: < Preparation Example 1 > Preparation of rubber graft copolymer (A-1): ^ Heliconia pine 1, 3-butadiene 150.00 Peroxyacid evaluation solution (U) 15.00 Page 16 This paper size is used in China National Standard (CNS) A4 specification (210X297mm) I. Batch '^. Order each (please read the notes on the back before filling this page) Printed Α7 Β7 by the Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs (Lki) Dodecyl sulfate reed solution (ίου 20.00 Distilled water 190.00 Ethylene glycol dimethacrylate 0.13 According to the above formula and reacted at 65t inversion temperature for 12 hours, the conversion rate is 94¾, the solid content is about 40S ;, synthetic rubber emulsion with a weight average particle size of 0.1%. In addition, ionic coagulants containing carboxylic acid groups are manufactured with the following ingredients: ^ _iiL weight__ parts ethyl acrylate 90.0 acrylic acid 10.0 potassium persulfate solution (U) 0.5 Sodium dodecyl sulfate solution (10¾) 0.5 Distilled water 200.0 Reaction at the reaction temperature of 75 ° C for 5 hours according to the above formula, to obtain a carboxylic acid group-containing ion molecular coagulant with a conversion rate of about 95¾ and a pH value of 6.0. Use 3 parts by weight of carboxylic acid group Molecular aggregating agent (dry weight) is used to fatten 100 parts by weight of synthetic rubber emulsion. The pH value of the resulting hypertrophic rubber emulsion is 8.5, and the average particle diameter of its rubber particles is about 0.31 / ύΠ. The aforementioned hypertrophic rubber emulsion is grafted and polymerized according to the following formula to make the rubber graft copolymer (Α-1). Ordering (please read the precautions on the back before filling out this page) Emulsified rubber emulsion (dry weight) 100.0 Styrene 25.0 Page 17 The paper size is applicable to China National Standard (CNS) Α4 specifications (210Χ 297 mm) Employee Consumer Cooperation Du Printed A7 _B7_ V. Invention Description (lb) Acrylonitrile 8.3 Tertiary-dodecyl mercaptan 2.0 Cumene hydroperoxide 3.0 Ferrous azemic acid solution (0.2¾) 3.0 Formaldehyde-formed hyponitric acid pin solution (10¾) 0.9 Ethylenediamine Tetraacetic acid solution (0.25S :) 3.0 The rubber graft copolymer emulsion prepared according to the formula in the above table is dehydrated and dried to a moisture content of 23; the following can be used to produce the oak seedling graft required by the present invention Copolymer (A-1) (rubber content 75 weight Amount X), the weight average particle size of the rubber particles is 0.31 nanometers, and the graft ratio is 30.5¾. The molecular weight of the styrene-propylene-S copolymer grafted on the rubber mash is 63,000. < Preparation Example 2 > Preparation of rubber graft copolymer (A-2): < Preparation Example 1 > The prepared synthetic rubber emulsion (the weight average particle size of the rubber particles is 0.1%), that is, without the hypertrophy process of the polymer coagulant, graft polymerization and inversion are directly carried out with the following formula , To prepare the rubber copolymer (A-2) 〇 ^ _ parts * m_m synthetic rubber emulsion (0 1 扉) (dry weight) 100.0 styrene 20.0 propylene I Yu 8.3 methyl methacrylate 5.0 third level Dodecyl Mercaptan 2.0 Diisopropylbenzene Hydrogen Peroxide 3.0 Ferrous Sulfate Solution (0.2 2¾) 3.0 Page 18 This paper size is based on China National Standard (CNS) A4 (210X297mm) I Preparing (please read the precautions on the back and fill in this f) A7 Β7 printed by the consumer cooperation of the Central Standards Bureau of the Ministry of Economy V. Invention Instructions (! 7) Sodium formaldehyde solution (ΙΟϋί) 0.9 Ethylenediamine Tetraacetic acid solution (0.25Χ) 3.0 The same as the rubber graft copolymer emulsion prepared < Preparation Example 1 > After treatment, the weight average particle diameter of the above rubber graft copolymer (Α-2) (rubber content 75 weight X) is 0.1 μm, the graft ratio is 26.8¾, the grafted styrene 1 Acrylonitrile monomethyl methacrylate copolymer has a molecular weight of 58,000. < Preparation Example 3 > Preparation of acryl-based copolymer (B-1): 75 parts by weight of styrene, 18 parts by weight of acrylonitrile, and 32 parts by weight of methyl methacrylate were fed at a rate of 12 kg / hr Mix, and then combine ethylene distearyl phenylamine 3.0 g / hr, dibenzoyl carboxide, tertiary-dodecyl mercaptan, and the recovery liquid described later as a feed solution to the interior to maintain the temperature at 108 t and a 45-liter volume kettle-type polymerization tank with an agitator, and keep the proportion of formazan in the reaction liquid at 15 S; and the polymerization rate is kept at 55¾. After the reaction liquid is removed through the devolatilization device , The particles of the propylene-based strip copolymer required by the present invention can be obtained; on the other hand, the volatile components removed are condensed by a condenser as a recovery liquid, and it is continuously used with the aforementioned raw material mixed liquid; this method can be used by dibenzene Adjust the reaction rate with the amount of formaldehyde pergasification, or adjust the amount of tertiary-dodecyl mercaptan; finally make styrene-propylene U-Shou-methyl with a melt flow index of 1 at a rate of about 12kg / hr Methyl acrylate copolymer (B-1). < Preparation Example 4 > Preparation of acryl-based copolymer (B-2): Methyl methacrylate (trade name: ACRYREX CM-205) manufactured by the applicant company was directly used. Page 19 This paper uses the Chinese National Standard (CNS) M specifications (210X297mm) --------- meal ------ ΪΤ ------ i (please read first Note on the back and then fill out this page) A7 B7 I printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-___ ____ _________ ____ V. Description of Invention (s) < Preparation Example 5 > Graft copolymer ((:): Use 7 parts by weight of polybutadiene (produced by Asahi Kasei Corporation, trade name-Asadene 55AS) as diene strip rubber, 0.1 parts by weight of third -Dodecyl mercaptan and 0.07 parts by weight of dibenzoyl percarbate as the initiator, and 1.4 parts by weight of the gum graft copolymer (A-1) (75% by weight of rubber) and 1.4 parts by weight of acryl-based polymer (B-1) is completely dissolved in 74.4 parts by weight of styrene, 25.6 parts by weight of acrylonitrile and 30 parts by weight of ethylbenzene to form a feed solution; It is fed into the first reactor in series, the body width of this first reactor is 44 liters, the reaction temperature is 100t, and the spiral type «mixing device * with a mixing speed of 300 r * f > ia, Yu Zhuang A cooling circulation pipe is provided in the mixing device, and the mixture after the reaction in the first reactor is continuously taken out and sent into the second reactor. The device in the second reactor is the same as the first reactor, and the conversion rate of the mixture reaches At 60 ×, the mixture is taken out to the devolatilization device to remove unreacted monomers and volatiles. After granulating S, the graft copolymer (C-1) with a weight average particle diameter of 1.1 / a can be prepared. According to the aforementioned preparation method and the proportions set out in Table 1, grafts are produced Copolymers (C-2), (C-3), (C-4), (C-5), (C-6). < Preparation Example 6 > Preparation of graft copolymer (丨)): Synthetic rubber emulsion is the same as that in Preparation Example 1, but the hypertrophy treatment is changed to 3.5 parts by weight of a carboxylic acid group-containing polymer coagulant to enlarge 100 parts by weight Synthetic rubber emulsion, the pH value of the obtained rubber emulsion is 8.5, and the weight average particle size of the rubber particles is about 0.28%, and the graft polymerization is carried out according to the following formula to obtain the graft copolymer ( D). Page 20 This paper standard uses the Chinese National Standard (CNS) A4 specification (210X297mm). T each (please read the precautions on the back before filling out this page) The Ministry of Economic Affairs Central Standard Falcon Bureau Employee Consumer Cooperative Printed A7 B7 Fifth, the description of the invention (θ) ^ _iit heavy latex rubber emulsion (dry weight) 100. Styrene 40. Acrylonitrile 13. Third-grade dodecyl mercaptan 2.0 Cumene hydrogen peroxide 3.0 Sulfuric acid Ferrous solution (0.230 3.0 Sodium formaldehyde sulfoxylate solution (10X) 0.9 Ethylenediaminetetraacetic acid solution (0.253!) 3.0 The weight average particle size of the above graft copolymer (D) (rubber content 65 weight ") is 0.28 The grafting rate is 42 X, and the molecular weight of the grafted styrene-acrylonitrile copolymer is 80,000. < Preparation Example 7 > Preparation of copolymer (E): 76 parts by weight of styrene and 24 parts by weight of acrylonitrile were mixed at a rate of 12 kg / hr, and then 3.0 g of ethylene distearate amide hr, dibenzoyl percarbate, tertiary-dodecyl mercaptan, and the volatiles removed by the reaction described below are condensed and the recovered liquid formed after condensation is used as the feeding liquid, as in the polymerization procedure of Preparation Example 3 A styrene ethyl acrylonitrile copolymer (E) having a melt flow index of 1.2 was obtained. The test standards for physical properties and molded appearance obtained in the following examples and comparative examples are as follows: Incoming impact strength: tested in accordance with the provisions of ASTM D-3763, expressed in kg.cn. Incoming chicken flammability test: According to the American UL-94 vertical burning test (thickness 1/16 English, page 21, the paper size is applicable to China National Standard (CNS) Α4 specification (210X297mm) -------- -f ------ lsτ ------ # (Please read the precautions on the back before filling in this page) Employee consumption cooperation of the Central Falcon Bureau of the Ministry of Economic Affairs Du Printed A7 B7 ------- Fifth, the invention description (π) inch method is implemented, Ο indicates that the test passed the test, and X indicates that the tide test was not passed. * Heat resistance test: tested in accordance with the provisions of ASTM D-1525. * Gas scorch resistance test: Under fixed conditions, the chess tool adopts Pin gate mold during injection molding, the material temperature is set at 250Ό, and the molded product obtained from the inspection produces gas burn marks. The symbol meaning in Table 2 is: : 〇 means no gas burn marks, X means serious gas burn marks. The appearance of the finished product: the test Η of the molded product is visually inspected, the flat appearance is indicated by ○, and the surface has granular protrusions or fish eyes are indicated by X. Rich case < Example 1 > 30 parts by weight of the graft copolymer (C-1), 25 parts by weight of the graft copolymer (D), 45 parts by weight of the copolymer (E), and bromine Austenitic ring gas type resin flame retardant with a content of 59¾ (product of the Japanese DIC company, trade name EC-14U6.4 parts by weight, 8 parts by weight of dibasic trioxide (Sba〇3), 10 parts by weight of atmospheric polyethylene), Dry mix with the Hanganer mixer, then use the two-column extruding mechanism with the cylinder temperature set at 205 and the die temperature set at 220C to obtain a granular flame-retardant styrene strip resin. The results of the tests are shown in Table 2. < Example 2 > The operating conditions are the same as those in Example 1. Extruded and granulated according to the formula in Table 2 and tested for molding test. The physical properties measured are also shown in Table 2. < Example 3> The operating conditions are the same as those in Example 1, except that the paper content of the tetrabromobisphenol with a bromine content of 59 «on page 22 is applicable to China National Standardization (CNS) A4 specifications (210X297 mm) ---- ----- Installed ------ Line (please read the precautions on the back before filling in this page) Α7 Β7 Ο. Fifth invention description (two 丨) A chicken burning agent (product of GREAT LAKES company. Goods Named BA-59P) instead of the Australian epoxy resin of Example 1, and extruded, granulated and subjected to various physical property tests according to the formula in the second table. The measured physical properties are also shown in the second table. < Example 4 > The operating conditions are the same as in Example 1, except that the bromine content of 59¾ tetrabromobisphenol A flame retardant (product of GREAT LAKES company. Trade name BA-59P) is used to replace the bromination of Example 1 The ring-type resin is extruded, granulated and subjected to various physical property tests according to the formula in the second table. The measured physical properties are also listed in the second table. < Example 5 > The operating conditions are the same as those in Example 1, and extruded and granulated according to the formula in the second table, and the test M for molding test is carried out. The measured physical properties are also shown in the second table. < Example 6 > The operating conditions are the same as those in Example 1, except that the flame retardant is a brominated ring gas type resin with a bromine content of 59¾ and decamodiphenyl SMDeca brorao diphenyl oxide (Deca for short). Various physical property tests were carried out, and the measured physical properties are also listed in Appendix 2. <Comparative Example 1> The same operating conditions as in Example 1, but without adding the graft copolymer (C), the finished product was also subjected to various physical property tests, and the results are also shown in Appendix 2. < Comparative Example 2 > The same procedure as in Example 1, except that the propylene-based copolymer (B) was not added to the graft copolymer (C), and the physical properties of the formed Lan test Η were also measured and contained in Attached in the second table. < Comparative Example 3 > Page 23 This paper standard uses the Chinese National Standards (CNS) Α4 specification (210X297 turbulence) --------- Installation ------ Threading (please first Read the precautions on the back and fill in this tile) Employee consumption cooperation of the Central Falcon Bureau of the Ministry of Economic Affairs Du Printed Central Sample Falcon Employee Consumer Cooperative of the Ministry of Economic Affairs Printed A7 B7__ V. Invention description (&) Same operation as Example 1 Conditions, but rubber graft copolymer (A) and propylene-based strip copolymer (B) are not added to the graft copolymer (C). The cracked finished products are also subjected to various physical properties tests. The results are also shown in Appendix 2. < Comparative Example 4 > The operating conditions are the same as in Example 1, but the graft copolymer (D) is not added. The finished product is also subjected to various physical property tests, and the results are also shown in Appendix 2. < Comparative Example 5 > The operating conditions are the same as in Example 1, but the addition of chicken burning agent is less than 5 parts by weight, and the resulting finished product is also subjected to various physical property tests. The results are also shown in Appendix II. < Comparative Example 6 > The operating conditions are the same as in Example 1, but the added graft copolymer (C) is overlaid, and the finished product is also subjected to various physical property tests. The results are also shown in the attached table. The test result of Example 1 shows that if the graft copolymer (C) is not added to the resin composition of the present invention, not only the heat resistance and surface impact strength of the resin are poor, but also the gas burn marks of the molded product are heavy. The test results show that when the graft copolymer (C) does not contain the propylene-based copolymer (B), the appearance of the molded product is poor, and when the graft copolymer (C) is not added with the rubber graft copolymer ( A) and propylene-based copolymer (B), the surface impact strength of the resin is not good, which can be seen from the test results of Comparative Example 3; when the graft copolymer (D) is missing in the resin composition, the surface of the resin The impact strength is obviously insufficient, which can be proved by the test results of Comparative Example 4; and the test results of Comparative Example 5 show that when the amount of chicken fuel in the resin composition is insufficient, its flame retardance cannot pass through the paper on page 24 The scale selection uses the Chinese National Standard (CNS) A4 specification (210X29 * 7mm) ------- -^ .------ 1T ------ 0 (Please read the precautions on the back before filling in this page) A7 B7 V. Description of invention (β) Tested, but when graft copolymer ( C) When the addition of Dong exceeds 60 weight S :, it will cause the phenomenon of poor surface impact strength, which can be proved by the test results of Comparative Example 6. Looking again at Jia Shi Examples 1 to 6, the present invention is indeed able to make the resin have good flame resistance, high heat resistance, and also have excellent surface impact strength, gas burn resistance and The molded product has excellent appearance and other properties, so as to improve the physical properties of the flame-retardant styrene resin composition, and can be used in the industry. It has filed an application for an invention patent according to law. However, the above are only a few of the preferred and feasible embodiments of the present invention. Anyone who is familiar with this skill and who makes modifications or changes in accordance with the spirit of the present invention should be included in the patent application for this case. Attached Table 1: The composition and usage of the graft copolymer (C) used in the examples and comparative examples of the present invention. Attached Table 2: The components of the examples and comparative examples of the present invention, the use of each component, and the results of physical property tests. (Please read the precautions on the back before filling this page) Du Yinzhen, Employee Consumption Cooperation of the Central Standard Falcon Bureau of the Ministry of Economic Affairs Page 25 This paper scale is applicable to the Chinese National Standard (CNS) A # specification (21〇χ297 mm)
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