200415093 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種淸淨室用容器。更詳細而言，本 發明係關於一種由在芳香族乙烯單體、和可共聚合之其 他的單體所構成的母料樹脂中，分散有以二烯單體爲主成 分聚合而成的二烯系橡膠粒子所構成之熱可塑性樹脂形 成，該熱可塑性樹脂之灰分係在0.2重量％以下之淸淨室 用容器。 【先前技術】 爲了防止半導體製造硏序中矽晶圓、液晶面板製 造程序中之玻璃基板、硬碟製造程序中金屬碟片等之 污染’因而藉以淸淨室來處理之。在此等製造程序中， 爲使能效率良好地處置此等基板因而使用各種之容 器°例如’有同時地收容複數枚之基板，從淸淨室內 特定的製程輸送到下一個製程情況下使用的容器之情 形’也有收容在容器中而就地實施各種處理之情形。 被使用來做爲容器材質之樹脂，端視彼等之目的 而定有各式各樣。例如，聚丙烯雖然便宜，然而不能 使用於要求透明性、成形時之尺寸精度、剛性等用途 上。聚殘酸酯雖然透明且耐衝擊性均優，但是要能保 ί寸原來之h明性地進行靜電防止處理卻有困難，因而 樹脂成本咼。又，丙烯腈_苯乙烯共聚物（ABS樹脂）及 甲基丙細6$：甲酉曰-本乙嫌（M S樹脂）雖然是透明的，然 200415093 而除了耐衝擊性差以外，尙容易由於滑動擦而生磨損， 特別是難以使用於嫌棄污染之淸淨室內。又且，聚對 献酸丁二醇酯（PBT)及聚醚醚酮（PEEK)雖然耐熱性良 好’但是不透明且樹脂成本也高。 丙烯腈-丁二烯-苯乙烯（以下，稱爲A B S )及類似 於彼等之樹脂’在成形時之尺寸精度、成形品表面之 平滑性、剛性、耐衝擊性等之平衡上優異，而且一種 樹脂成本比較低的泛用樹脂。如以下所述這樣，也能 夠提供永久靜電防止性及處理性。 例如’在特開平9-9271 4號公報上設載著一種成 疋开狀之半導體晶圓收納用靜電防止容器。在該公報 之實施例中記載著一種使用ABS系永久靜電防止樹 脂’以2 3 0至2 4 0 °C射出成形之容器的例子（實施例1、 3及4)。在實施例中所記載的容器係具有良好的靜電 防止性，而且依商品別而定透明性也均優異（實施例 3)。 在特開平62-1 1 9256號公報上記載著一種於橡膠 質聚合物存在之下，於（甲基）丙烯酸酯單體及可共聚 合之其他的乙烯系單體構成的共聚物混合物予以接枝 聚合而成之聚合物中，摻混聚醚酯醯胺而形成的熱可 塑性樹脂組成物。也記載著此種樹脂組成物在永久靜 電防止性、耐衝擊性及透明性上均優異，而且可以被 使用於防止因靜電而起之障害的用途上，例如，可以 200415093 使用於I c載體容器。 又，特開平9-59462號公報上記載著—種殘留苯 乙烯系單體及殘留4 -乙烯環己烯中任何一種均在—定 量以下，而且橡膠粒子之平均粒徑及其分布均在一定 範圍的A B S樹脂組成物。使用此等樹脂組成物的話， 則可製做出一種衝擊強度及拉伸強度均優異，且具備 良好的光澤之無臭品。於該公報上也記載著AB S樹脂 可使用於家電製品之外殻及車輛成形品上。 依照特開平9-9271 4號公報及特開昭62-1 1 9256 號公報上記載，已知一種由ABS樹脂所形成的半導體 晶圓收納用靜電防止容器。但是，做爲使用於淸淨室 用容器的樹脂，ABS及其類似的樹脂，現實上的實際 情形則是差不多均未被使用。其大部分的理由之一， 是因爲具有以下所說明的污染源之問題。 就被使用於淸淨室內之容器而言，被收納的物品 大多數的情況是極度地排斥污染，因而容器不能成爲 彼等之污染源這一點是非常重要的。在污染物中特別 必要注意的是因金屬離子而引起的污染。例如，就半 導體製造程序而言，會擔心於擴散作業中，該等金屬 離子之不純物會擴散電路內而使得不良率增加。又且， 有必要同時地防止金屬離子以外的有機物所引起的污 染。 然而，製造AB S樹脂上之代表性方法，係爲一種 200415093 包括將藉由乳化聚合而得到的二烯系橡膠粒子，於乳 化液中接枝改性的製程。爲使在乳化液中之聚合反應 圓滑地進行，因而就必須要有多量的乳化劑，彼等在 大多數的情況是一種由金屬鹽所構成的界面活性劑。 又，將所得到的接枝化橡膠粒子予以凝固而有需要從 乳化液中分離出來，但此時多半的情況是鹽析之，在 此種情形下凝固物中就會更進一步地含有多量的鹽。 結果，在市面上所販售的A B S樹脂多半殘存有相當量 的金屬鹽成分。因而，就對於具有成爲污染源之可能 性的物質就敬而遠之，以致現今幾乎不採用A B S及其 類似之樹脂來做爲淸淨室用容器之素材。 又，在特開平9-59462號公報上雖然記載著一種 殘留有機物少的A B S樹脂，然而做成家電製品之外殻 及車輛成形品會有惡臭問題，更不用說會有成爲淸淨 室內之污染源的問題。 本發明即是用以解上述之課題，而以提供一種由 ABS及其類似的熱可塑性樹脂構成，且該熱可塑性樹 脂之灰分少、因金屬離子污染的可能性低之淸淨室用 容器爲目的。 一種淸淨室用容器，係由在芳香族乙烯單體、和可 共聚合之其他的單體所構成的母料樹脂中，分散有以二烯 單體爲主成分聚合而成的二烯系橡膠粒子所構成之熱可塑 性樹脂形成，該熱可塑性樹脂之灰分係在〇 · 2重量％以下。 -9- 200415093 一種非常適合於收納從半導體基板、顯示裝置基板及記錄 媒體基板中所選擇的板狀體之容器。藉此，提供一種由 A B S及其類似的樹脂所形成，但灰分最少難以成爲金 屬污染源的淸淨室用容器。 【發明內容】 上述之課題係可藉著提供一種由在芳香族乙烯單 體、和可共聚合之其他的單體所構成的母料樹脂中，分散 有以二烯單體爲主成分聚合而成的二烯系橡膠粒子所構成 之熱可塑性樹脂形成，該熱可塑性樹脂之灰分係在〇 . 2重 量％以下之淸淨室用容器而達成。 此時’前述可共聚合之其他的單體，理想上是從氰 化乙烯單體及不飽和羧酸烷酯單體中所適當地選出之至少 一種。又且，前述熱可塑性樹脂理想上是一種由 5〜50 重量％之二烯系橡膠、1〇〜90重量。/。之芳香族二烯單體 及10〜90重量。/。之前述可共聚合之其他的單體聚合而 成之物。 前述熱可塑性樹脂之實施態樣，是在分散有將二 烯予以二烯單體予以聚合而成的二烯系橡膠粒子之乳化液 中，將由芳香族乙烯單體、和可共聚合之其他的單體所共 聚合而成的接枝樹脂、和由另類的芳香族乙烯單體、和可 共聚合之其他的單體所共聚合而成的樹脂予以熔融混合而 得之物。又且，此時，使用少量的酸而將接枝共聚合 樹脂粒子予以凝固、經洗淨然後再供給到熔融混合比 -10- 200415093 較理想。 又’則述熱可塑性樹脂爲一種將由二烯單體聚合 而成的二烯系橡膠予以溶解在芳香族乙烯單體、和可共 聚合之其他的單體中，然後使前述之芳香族乙烯單體、和 與此等可共聚合之其他的單體聚合而得到之物，也是理 想的實施態樣。 前述之二烯單體理想上係爲1,3_丁二烯，且前述熱 可塑性樹脂之4-乙烯環己烯含有量係在1〇〇 ppm以下。 前述熱可塑性樹脂理想上爲含有一種由聚醚酯醯胺所形 成的靜電防止劑、或者含有一種由導電性碳所構成的靜電 防止劑。理想上，將由成形品所切削出的試料於1 5 0 保 持10分鐘之後，在10分鐘內所產生的有機氣體量之苯 乙烯換算値係在600 ppm以下。理想上，前述熱可塑性 樹脂係一種在做成3毫米厚度之射出成形品時的霧値爲 20 %以下之樹脂。又且，理想上，爲一種將射出成形時之 滚筒設定溫度設在2 2 0 °C以下再予以射出成形而成之物。 本發明理想的實施態樣，係爲一種供收納從半導 體基板、顯示裝置基板及記錄媒體基板中所選擇之板狀體 用的上述之淸淨室用容器。 【實施方式】 以下，就詳細地說明本發明。 本發明之淸淨室用容器，係爲一種由在芳香族乙 烯單體、和可共聚合之其他的單體所構成的母料樹脂中， 200415093 分散有由二烯單體聚合而成的二烯系橡膠粒子所構成之熱 可塑性樹脂而形成之物。 使用於本發明之熱可塑性樹脂，係爲一種芳香族 乙烯單體 '和可共聚合之其他的單體間之共聚物所形成 之物。不是一種僅由芳香族乙烯單體所構成之聚合物， 藉著與其他的單體形成共聚物，可容易地做成符合需 要之耐衝性、透明性、耐熱性、耐藥品性等均優異的 樹脂。該等聚合物通常是一種無規共聚物。 此處所使用的芳香族乙烯單體，舉例來說，例如 是苯乙嫌、甲基苯乙燒、對甲基苯乙燃等，可以使 用此等中之1種或2種以上。可共聚合之其他的單體， 只要是能夠與芳香族乙烯單體共聚合者即可，並沒有 特別地限定，舉例來說’例如其可以是以丙烯腈、甲 基丙烯腈等之（甲基）丙烯酸酯爲代表的胺化乙烯單 體，以甲基丙烯酸酯、乙基丙烯酸酯、甲基甲基丙 烯酸酯、乙基甲基丙烯酸酯等之（甲基）丙烯酸酯爲代 表的不飽和殘酸院酯單體，丙烯酸、甲基丙條酸、馬 來酸、馬來酸酐、檸康酸酐等之不飽和羧酸或不飽和 二羧酸酐單體，馬來醯胺、甲基馬來醯胺、乙基馬來 醯胺、Ν -苯基馬來醯胺、Ο -氯-Ν ·苯馬來酸醯胺等之馬 來醯胺系單體等。此等可共聚合之其他的單體，也是 可以使用1種或2種以上。 然而，在此等之中，前述可共聚合之其他的單體， 200415093 理想上是從胺化乙烯單體及不飽和羧酸烷酯單體中所 選取之1種以上。藉由與胺化乙烯單體共聚合，以提 昇而性、耐藥性、剛性及尺寸安定性。又且，藉由與 不飽和羧酸烷酯單體共聚合，以提高透明性、硬度及 剛性。較宜是將此等兩者一起共聚合。 本發明中使用的熱可塑性樹脂，係在前述母料樹 脂中分散有由二烯單體聚合而成之二烯系橡膠粒子之 物。此時，橡膠粒子中的二烯單體之比例，較宜是在 鲁 5 〇重量％以上，更宜是在8 0重量％以上。被使用來做 爲二烯單體，舉例來說，例如其可以是1,3 -丁二烯、 異丙烯等，又使用其中之1種或2種以上均可以。然 而’在此等之中，理想上係使用性能上優異且低成本 的1，3 - 丁二烯。具體的聚合物，舉例來說，例如聚丁 二烯橡膠、苯乙烯-丁二烯橡膠（SBR)、丙烯腈-丁二烯 橡膠（NBR)、聚異丙烯橡膠等，特別是聚丁二烯橡膠 乃爲一種可以提低溫耐衝擊性等之優異的樹脂，而且 鲁 成本也低最爲理想。就上上述橡膠粒子之平均粒徑而 論’雖然也是沒有特別地限定，然而較宜是〇 . 〇 5〜1 0 微米，更宜是〇·〇8〜5微米。 就使用於本發明的熱可塑性樹脂之組成比例而論 也是沒有特別地限定，然而理想上是一種由5〜5 0重 量％之二烯系橡膠、10〜90重量。/。之芳香族二烯單體及 10〜90重量％之前述可共聚合之其他的單體聚合而成 -13- 200415093 之物。此種組成比例，係爲表示在最終成形品內之熱 可塑性樹脂中的各成分的比例，例如，在預先以預定 量的芳香族二烯單體及可共聚合之其他的單體將二烯 系橡膠予以改性之後，更進一步地與另外聚合之芳香 族一嫌單體及可共聚合之其他的單體構成之共聚物一 起熔融混合物的情況下，則係表示混合物總量之比例。 二烯系橡膠之含量較宜是5〜50重量。/。。當在小於 5重量％之情況下，則會有耐衝擊性不夠充分的情形， 因而較理想上是在1 0重量％以上。相反的，當超過5 0 重量％時，剛性或成形性恐怕會下降，因而較理想爲 在3 0重量％以下，更理想是在2 0重量％以下。又， 芳香族乙烯單體來源成分之含量，較宜是在彳〇〜90重 量％。當小於1 0重量。/。之情況下，剛性或成形性恐怕 會下降，因而較理想爲在2 0重量％以上。當在超過9 0 重量％之情況下，耐衝擊性恐怕會下降，而較理想是 在80重量％以下。尤其，在要求透明性的情況下，較 宜是在50重量。/。以下，更宜是在30重量。/。以下。 可共聚合之其他的單體來源成分之含量較宜是在 1 0〜90重量。/。。比較理想是在20重量。/。以上，又且在 8 0重量％以下。尤其，在特別要求透明性的情況下， 可共聚合之其他的單體較宜是含有不飽和羧酸烷酯單 體來源成分，且其含量較宜是40〜80重量。/。。藉由此 種作法’可以使得母料樹脂和橡膠粒子間的折射率差 -14- 200415093 變小，而且可以使得樹脂全體均爲透明。 使用於本發明中的熱可塑性樹脂之製造方法並沒 有特別地限定，可以藉由利用乳化聚合、懸濁聚合、 塊狀聚合、溶液聚合、或此等之組合而成之聚合方法 製造而得。然而，在此等之中，對二烯系橡膠而言， 雖然是含有芳香族乙烯單體和可共聚合之其他的單體 予以接枝共聚合之製程，然而，就橡膠粒子之分散性、 及橡膠粒子和母料樹脂間之界面的強度等觀點來看， 0 則是較佳的。 在將二烯系橡膠予以改性之際，可以在含有橡膠 之乳化液（乳膠）殺予以接枝改性，也可以在將橡膠予 以溶解之溶液中予以接枝改性。 理想之製造方法之一，係爲一種分散有以二烯單體 聚合而成的二烯系橡膠粒子之乳化液中，將芳香族乙烯單 體、和可共聚合之其他的單體予以共聚合所構成的接枝共 聚合樹脂、另外的芳香族乙烯單體和可共聚合之其他的單 · 體予以共聚合而成之樹脂，一起熔融混合之方法。在乳化 液中進行接枝共聚合的情況下，橡膠組成、粒徑、溶膠含 有率等之控制容易，而且也可輕易得到透明性、耐衝擊性 及成形性均優異的高性能樹脂。又且，將在乳化液中所合 成的接枝共聚合樹脂粒子，藉由另外之塊狀（或溶液）聚合 而成之共聚物予以稀釋，可以減少乳化液來源之金屬鹽成 分量。 -15- 200415093 就上述製造方法而言，雖然在乳化聚合製程中可以 使用乳化劑、聚合起始物、鹽析劑等之各種的添加劑，然 而大多數情況此等多半爲金屬鹽，其會有容易混入最終製 品之問題。在乳化聚合中，有必要使用和乳化劑相當之量， 然而此等之中多半是使用高級脂肪酸的鹼金屬鹽及硫酸的 鹼金屬鹽等。又，做爲乳化聚合中的聚合起始劑，雖然可 以使用過氧化物等，然而也有使用有機氫化過氧化物之乳 膠系起始劑，在此種情況下多半是使用鐵鹽等。更且，在 乳化聚合之後將所得到的接枝共聚合樹脂粒子予以凝固之 際’也多半是添加高濃度之鹼金屬鹽及鹼土金屬鹽再予以 析出的情形。 從而，爲了降低在最終製品中之金屬離子含有量， 即灰分，在上述乳化聚合後之凝固製程中，較宜是使用酸 使之凝固，可以使用的酸，舉例來說，例如其可以是鹽酸 及硫酸。此時，倂用輔助性鹽類也沒有關係，然而較宜是 不使用鹽類，而僅以酸將之凝固。藉由此種作法，可以避 免在凝固製程中混入金屬鹽。又，爲了凝固後之洗淨條件， 較宜是不只增加洗淨水之量而且也增加洗淨次數。尤其， 洗淨水宜是在與給予洗淨之接枝共聚合樹脂粒子之視體積 相同體積以上，較宜是使用2倍以上，更宜是3倍以上 體積。又，較宜是進行洗淨-脫水步驟2次以上，更宜是 反復地進行3次以上之洗淨。在一般之ABS樹脂的製造 程序中，依照經濟性之觀點來看，洗淨-脫水製程通常是 -16- 200415093 不進行複數次反復操作。 如以上所述，使用少量的酸將乳化聚合後之接枝聚 合樹脂粒子予以凝固，並充分地洗淨後，再與另外的塊狀 (或者溶液）聚合之共聚物一起熔融混合，藉此可以有效率 地降低灰分。熔融混合之方法並沒有特別地限定，可以使 用押出機、斑伯理混合機、輥、捏和機等公知的混煉裝置 予以混合。此時，可以同時地與靜電防止劑等之其他成分 一起混合。 0 其他理想的製造方法之一，係爲一種將由二烯單體 聚合而成的二烯系橡膠予以溶解在芳香族乙烯單體、和 可共聚合之其他的單體中，然後使前述之芳香族乙烯單 體、和與此等可共聚合之其他的單體聚合予以聚合之方 法。此時’可以採用在不含有他種溶劑之狀態下聚合 之塊狀聚合方法，也可以採用在他種溶劑，例如乙基 苯之存在狀態下聚合之溶液聚合方法，採用任何一種 均可以。 · 依照此等方法，可以不經由乳化聚合製程而製造出 於本發明中使用的熱可塑性樹脂，且可以減少由乳化劑及 鹽析劑而來的金屬鹽之殘存量。此種製造方法，因爲不容 易控制橡膠粒子之粒徑及組成，因而與具有乳化聚合製程 的製造方法比起來，在大多數的情況下透明性及耐衝擊性 等會變得不夠充分，因而現在必然不是一種廣泛實施的製 造方法。然而，由於能夠減少殘存金屬鹽之量，因而對本 -17- 200415093 發明之用途而言是一種較佳的方法。 使用在本發明中的熱可塑性樹脂之灰分係在0·2重 量％以下。當該灰分超過2重量％時，在淸淨室內之金屬 離子就容易成爲污染源，因而不宜。例如，在半導體製造 工程中，只要是直接與如晶圓載體等之晶圓接觸的容器， 就有成爲晶圓之直接污染源之情況，也有在處理水中溶出 金屬離子之情形。又，即使在藉由內包有載體的盒子以使 得容器不會直接與晶圓接觸之情況下，磨損的粉塵同樣會 附著在晶圓或載體上而產生不良的影響。尤其，關於半導 體製造程序方面，在藉由加熱而使物質擴散作業中，當該 金屬離子爲不純物時，恐怕就會擴散到電路內而使得不良 品率上昇。該熱可塑性樹脂之灰分較宜是在0.1 8重量％ 以下，更宜是在〇_ 15重量％以下。 又且，就使用於本發明中的熱可塑性樹脂而言，其 中所使用的二烯單體較宜是1,3-丁二烯，已如前述所說 明一般。此時，該熱可塑性樹脂之4-乙烯環己烯含量較 宜是在100 ppm以下。4-乙烯環己烯由於主要是在進行 二烯單體之聚合時的副產物，爲1，3-丁二烯之環狀二聚 物。因爲具有惡臭所以是一種不期望產生之物，特別 是在像淸淨室內這樣的封閉空間作業的情況下，此種 惡臭尤其容易形成問題。又且，在像淸淨室這樣的封 閉空間中，因爲揮發性有機物容易停留的緣故，所以 是一種污染源，因而不是一種理想的物質。4-乙烯環 200415093 己烯含量較宜是在8 0 p p m以下，更理想是在6 0 p p m以 下。 在具有乳化聚合之情況下，爲了降低1，3-丁二烯之 含量’較宜是於加熱乳化聚合後之乳化液，揮發除去 未反應之二烯單體、並同時揮發除去副生的4 -乙條環 己稀。加熱方法理想上採用水蒸氣蒸餾，較宜是在6〇 °C以上，更理想爲在7 0 °C以上的溫度，宜是在1 〇分鐘 以上’更理想爲30分鐘以上之時間來進行水蒸氣蒸餾 φ 操作。又’較宜是強化在乳化聚合後之凝固後的洗淨 條件。此時，較佳的洗淨條件，係如前述那樣。 又，就塊狀聚合或溶液聚合而言，較宜是藉由強 化脫除揮發分製程以減低4 -乙燦環己嫌之含有量。具 體而言，於聚合物終了之後，較宜是以1 8 0 °C以上、 更理想爲200 °C以上之溫度，減壓到1 00 To rr以下、 理想上在50 Torr以下，除去未反應之單體等、並同 時除去4-乙烯環己烯。在聚合時使用溶劑的情況下，雖 ® 然同時除去溶劑和4·乙烯環己烯，然而較宜是可以良好 的效率除去4-乙烯環己烯。 使用於本發明之熱可塑性樹脂，也可以含有各種添 加劑。在本發明說明書中，所謂的熱可塑性樹脂係包括含 有添加劑之組成物者。在各種之添加劑之中，譬如含有靜 電防止劑，因爲可以防止半導體晶圓之靜電破壞之特點來 看，以及依照可以防止微粒子之附著的觀點來看是較佳 -19- 200415093 的。 此種靜電防止劑，舉例來說，例如其可以是烷基胺 等之陽離子界面活性劑，高級醇之硫酸鹽、高級醇之氧化 乙烯加成物的硫酸酯鹽、烷基苯酚之氧化乙烯加成物的硫 酸酯鹽、鏈烷磺酸鹽、烷基苯并磺酸鹽、烷基硫化琥珀酸 酯鹽、伸萘磺酸弗爾酮縮聚物之鹽、高級醇之氧化乙烯加 成物之矽酸酯鹽、烷基苯酚之氧化乙烯加成物之矽酸酯 鹽、烷基苯酚之氧化乙烯加成物之矽酸酯鹽等之陰離子界 面活性劑，高級脂肪酸之山梨醇酯、高級脂肪酸之單甘油 醚酯、高級脂肪酸之單甘油醚的氧化乙烯加成物、高級醇 之氧化乙烯加成物、高級脂肪酸之氧化乙烯加成物、高級 醇之氧化乙烯加成物、醯胺氧化乙烯加成物、烷基醯胺之 氧化乙烯加成物等之非離子界面活性劑，聚伸烷基二醇、 聚烷基二醇系共聚物、聚醚酯醯胺、導電性碳等。可以使 用此等之1種或2種以上。 此等之中，較宜是使用聚醚酯醯胺。因爲聚醚酯 醯胺不會形成鹽，因而不必擔心溶出鹽。又且，分子 量比較高，且與使用於本發明之熱可塑性樹脂間之相 溶性也良好，所以不會滲出，所以可以長期地發揮靜 電防止效果。聚醚酯醯胺的具體例子，舉例來說，例 如將含有由碳原子數在6以上之胺基羧酸、碳原子數 在6以上之內酯及二胺和二羧酸所得到的碳原子在6 以上之鹽中所選出的至少1種之聚醯系化合物（A1 )及 -20- 200415093 二羧酸（A2)衍生而得到之兩末端羧基之聚醯胺（A)、和 聚氧伸烷二醇及/或聯苯酯類之環氧乙烷加成物所形成 的聚醚二醇（B)予以聚縮合而得到的化合物等。 更且，就要求透明性之情況而言，理想上聚醚酯 醯胺係被處理成具有與使用於本發明之熱可塑性樹脂 同樣的折射率。聚丁二烯之折射率爲1 . 52，因爲於要 求透明性時母料樹脂之折射率係被處理成和該折射率 一樣，所以聚醚酯醯胺之折射率在室溫下較宜是1 .48〜 1.56，更宜是1.50〜1_54，最適當爲1.51〜1.53。 又，若是不要求透明的用途的話，則較宜是使用 導電性碳做爲靜電防止劑。如後述這樣，於使用有機 化合物做爲靜電防止劑的情況下，不用說當然會擔心 在成形時熱分解。楣對於此，石墨粉末、碳黑、碳纖 維、碳奈米管等之導電性碳，在熱可塑性樹脂之熔融 成形時之溫度下幾乎是不分解的。從而，在像淸淨室 用容器這樣的嫌惡因揮發性有機物所引起的污染之用 途上，使用導電性碳粒子做爲靜電防止劑也是理想的。 再者，上述靜電防止劑之使用比例雖然並沒有特 別地限定，然而依照其物性平衡面而定，在本發明之 熱可塑性樹脂中較宜是含有1〜30重量。/。。 又且，使用於本發明之熱可塑性樹脂，在不妨害 本發明之效果的範圍內，也可以添加公知的添加劑， 例如，可視需要而添加氧化防止劑、紫外線吸收劑、 -21 - 200415093 平滑劑、著色劑、充塡劑等。但是，所謂難以產生污 染物質，當考慮於本發明之淸淨室用容器所要求的性 能時，較宜是將此種添加劑的使用量保留在最低限度 中〇 靜電防止劑等對於上述添加劑之摻混方法並沒有 特別地限定，可以使用押出機、斑伯里混合機、輥、 捏和機等，混合使用也可以。如前述，在將接枝共聚 合樹脂粒子、和另外的共聚合而成的樹脂予以熔融混 合物之情況下，爲了在進行熔融混合時，並同時地除 去揮發成分，則理想上實施脫除揮發分處理。脫除揮 發分處理方法，舉例來說，例如以在熔融狀態下進行 減壓是最爲適當的方法。 具體而言，較宜是使用具有減壓出口之擠壓機來 進行熔融混煉。擠壓機可以是單軸擠壓機，也可以是 雙軸擠壓機。又，出口可以不只設置在一個位置而設 置複數位置。此時，理想的熔融混煉溫度是1 60〜220°c。 又，藉著反復地進行此種脫除揮發分處理，可以進一 步減少樹脂中揮發成分之含量。例如，若使用具有減 壓出口之擠壓機來進行熔融混煉的話，較宜是將經熔 融混煉的板狀化物反復地進行再度熔融混煉。 被使用於本發明之熱可塑性樹脂之熔融流速（220 t、1 〇公斤荷重）雖然並沒有特別地限定，然而通常是 1〜1 00克/1 0分鐘。依照成形性的觀點來看，較宜是5 -22- 200415093 克/1 0分鐘以上，依照強度的觀點來看，較宜是在5 0 克/1 0分鐘以下。 又，關於本發明使用於要求內部視認性之用途上 的情況，熱可塑性樹脂較宜是透明物質。例如，像在 使用內包有矽晶圓載體之盒子這樣的情形。在此種情 況下，該熱可塑性樹脂，較宜是當做成厚度3毫米之 射出成形時之霧値爲2 0 %以下之樹脂。藉著使具有2 0 % 以下之霧値，不僅可以容易地從容器外部視認其內部， 而且外觀也美麗。又，例如，可以利用讀取裝置從外 部讀取貼附在載體上之矽晶圓等來進行生產管理。又， 若以全光線穿透率表現的話，較宜是在7 0 %以上，更 宜是在8 0 %以上。 使用此種作法所得到的熱可塑性樹脂，而形成本 發明之淸淨室用容器。成形方法並沒有特別地限定， 可以採用射出成形、擠壓成形、熔吹成形等之各種的 熔融成形方法。又，也可以對於一旦經擠壓成形的薄 片等實施熱成形等之二次加工。在此等之中，譬如以 淸淨室用容器而言，因爲多半是要求比較複雜之尺寸 精度，因而較宜是利用射出成形來進行成形。 射出成形時之成形條件也是沒有特別地限定，然 而較宜是使滾筒設定溫度在220 °C以下而成形。一般 將ABS樹脂予以射出成形之際，多半是以230 °C以上 之樹脂溫度進行射出成形，然而在本發明中藉由在2 2 0 -23- 200415093 °c以下，可望將樹脂之分解抑制到最低限度。在射出 成形之樹脂之熔融時間通常不是愈長愈好’於普通用 途上，考慮成形性及成形速度較宜是以足夠高溫來成 形；就供於淸淨室內使用目的而言’不僅可以減低因 熔融時之熱分解所發生的有機物量則是重要的。從而’ 較宜是將可能成形溫度下降到最低成形溫度。可能成 形溫度係因樹脂之組成及熔融流速而不同’考慮此等 因素而加以設定。例如，增加樹脂中的不飽和羧酸烷 酯單體由來成分之比例，可容易使得以比較低溫來成 形。射出成形時之滾筒設定溫度較理想的是在2 1 0 °C 以下，更理想的是在2 0 0 °C以下。又且，通常是在 1 6 0 °c以上。 另外，射出成形時之熔融樹脂溫度，也會對摻混 在樹脂中的添加劑之熱分解行爲產生影響。例如，使 用於本發明之淸淨室用容器的熱可塑性樹脂中，較宜 是含有靜電防止劑，其中較理想的是聚醚酯醯胺，已 經在前面說明了。熔融成形時，雖然是微量，但此種 靜電防止劑也會熱分解。此時，就以高溫成形而言， 因熱分解而發生的低分子量之胺及醯胺（包括內酯）的 量會增加。胺及醯胺會溶出於水中透過處理液而容易 污染半導體晶圓，更且由於含有此種氮元素之化合物， 在熱擴散處理等之半導體製造程序中，有可能產生氨 及胺等之鹼性物質的緣故，因而是比一般的僅由碳、 -24- 200415093 氫、氧所構成的有機化合物比起來更令人嫌惡的污染 源。從而’尤其是在使用含有像這樣的氮元素之靜電 防止劑時’較宜是儘可能以低溫成形。 以此種做法成形的本發明之淸淨室用容器中所含 有的分解有機物之量，較宜是儘可能地少。具體而言， 將從成形品切削出的試料於1 5 〇 °c下保持1 〇分鐘之 後，於1 〇分鐘內所產生的有機氣體量之苯乙烯換算値 較宜是在600 ppm以下。比較理想的是在400 ppm 以下’更理想的是在3 0 0 p p m以下。將分解有機物之 量減低到像這樣時，在製造如前述這樣的樹脂時就可 有效地減低揮發成分，並且同時有效地儘可能的低溫 來成形。 本發明之淸淨室用容器是一種可在淸淨室內使用 的容器’是一種收容原料、中間製品或製品用之容器， 並沒有特別地限定。舉例來說，例如是收納半導體基 板、顯示裝置基板及記錄媒體基板中所選出的板狀體 等之理想的物品用之容器。 半導體基板，舉例來說，例如積體電路製造用的 基板、太陽電池製造用之基板等。此種材料並沒有特 別地限定於以矽爲代表之物。又，其形態可以是像矽 晶圓這樣的圓形，也可以是像太陽能電池這樣的四方 形。又’將矽晶圓圓切斷成晶片的形態也沒有關係。 其中之代表性的實施態樣，係矽晶圓用容器。近 -25- 200415093 年來，矽晶圓已逸漸進行大口徑化，因應於此矽晶圓 用容器之尺寸也逐漸地變大。從而，既可以保持又不 會損傷尺寸大的容器之形態，理想上是使用一種剛性 及耐衝性均優的樹脂。依照此觀點來看，本發明之淸 淨室用容器最爲理想。又，隨著尺寸變大，因而對成 形品全體之尺寸精度之要求水準就變得嚴格，故可以 良好的尺寸精度成形之本發明的淸淨室用容器最理 想。從而，本發明之淸淨室用容器，理想上係使用於 6吋以上之矽晶圓，比較理想是使用於8吋以上之矽 晶圓，更理想是使用於300毫米以上之矽晶圓。 此時，在直接配列有矽晶圓之稱爲載體的容器之 情況下，因爲矽晶圓直接與載體接觸的緣故，所以金 屬污染特別容易成爲問題，而且容易透過處理液等產 生交錯污染。從而，對於像這種載體較宜是本發明之 淸淨室用容器。在此種情況下，使用可以視認內部之 透明樹脂特別佳。又，由於揮發成分容易充滿盒中， 因而較佳爲因臭氣成分等之揮發成分污染最少者。因 爲這樣，即使是對於同時擔任載體與盒子之一體成型 的容器，最理想亦是使用本發明之淸淨室用容器。 顯示裝置基板，舉例來說，例如液晶顯示裝置製 造用之基板、電漿顯示裝置製造用之基板、電致發光 顯示裝置製造用基板等。此等基板之代表性材料爲玻 璃，其他的物品，例如，透明樹脂等也沒有關係。在 -26 - 200415093 nt ®顯示裝置基板的情況下，也由於存在有畫素驅動 用之電路’嫌惡因金屬而來之污染，因而採用本發明 之淸淨室用容器較理想。又，因爲顯示裝置基板多半 是特大型的，所以和前述的大口徑之矽晶圓同樣地， 較宜是使用本發明之淸淨室用容器。 又’記錄媒體基板，舉例來說，例如硬碟基板及 光碟基板。在硬碟基板的情況之素材，以使用金屬及 玻璃爲代表，但並沒有特別地限定。又，在光碟基板 的情況之素材，以使用代表聚碳酸酯之透明塑膠爲代 表，但並沒有特別地限定。就此等之記錄媒體而言， 雖然記錄膜之組成依照其記錄形式而不同，由於近年 來記錄密度飛躍地提昇，即使只是少許的污染物質也 會對性能產生影響，因而使用本發明淸淨室用容器最 爲理想。 【用以實施發明之最佳形態】 以下，使用實施例更進一步詳細地說明本發明。 【合成例1】 在經氮取代之聚合反應器內，投入5 0份（固體物） 之聚丁二烯乳膠（重量平均粒徑爲0.3//，溶膠含量爲 8 5 % )、0.1份之乙烯二胺四乙酸鈉、〇 . 〇 〇 1部硫酸鐵、 〇. 3份之甲醛磺酸鈉，加熱至6 0 °C之後，再以3小時 連續地添加由3份之丙烯腈、1 2份之苯乙烯、3 5份 之甲基丙烯酸甲酯及0.2份之異丙苯過氧化氫所構成 - 27- 200415093 的混合物，更且進一步於6 0 °C下聚合之，而得到接枝 共聚物乳化乳膠。然後，再使用相對於1 0 0重量份（固 體物）之乳膠計爲0.3重量份之硫酸鎂鹽析之後，再加 入接枝共聚合樹脂粒子的1 .5倍體積之水，經攪拌再 予以脫水、洗淨後，再予以乾燥而得到接枝共聚合樹 脂粒子（1 )。 【合成例2】 除了變更在合成例1中之聚合後實施水蒸氣蒸餾 之點 '以及凝固及洗淨製程以外，與合成例1同樣的 做法而得到接枝共聚合樹脂粒子。也就是說，將水蒸 氣吹送入聚合後所得到的接枝共聚合乳膠中進行1小 時之水蒸氣蒸餾。此時乳膠的溫度爲8 0 °C。水蒸氣蒸 餾後，使用〇 · 1重量份做爲凝固劑予以凝固，更進一 步地加入接枝共聚合樹脂粒子的2.5倍之體積的水並 予以攪拌後，再進行脫水洗淨作業反復3次。除了上 之點以外，與合成例1同樣的做法而得到接枝共聚合 樹脂粒子（2)。 【合成例3】 在經氮取代之聚合反應器內，投入1 3 0份之純水 及0.3份之高硫酸鉀後，在攪拌下昇溫至6 5 °C。之後， 再以4小時分別地連續添加由1 0份之丙烯腈、3 0份 之苯乙烯、60份之甲基丙烯酸甲酯及0.35份之t-月 桂基硫醇所構成之混合單體、以及3 0份的含有2份 -28- 200415093 不均勻化松香酸鉀之乳化劑水溶液。然後，將聚合系 昇溫至7 0 °C，進行2小時熟成而得到苯乙烯系聚合物 乳膠。然後，再使用相對於1 0 0重量份（固體物）之乳 膠計爲2.5重量份之硫酸鎂鹽析之後，再加入苯乙烯 系聚合物的1 . 5倍體積之水，經攪拌再予以脫水、洗 淨後，再予以乾燥而得到苯乙烯系聚合物（3 )。 【合成例4】 使用容量爲20升之1座完全混合型反應槽而形成 之連續的聚合裝置，使用柱塞式泵以1 3公斤/小時連 續地供給由30份之苯乙烯、70份之甲基丙烯酸甲酯、 10重量份乙基苯、0.05重量份之t-月桂基硫醇、及 0.015重量份之做爲聚合起始劑的卜丁基過氧（2-乙基 己烷酯）所構成的聚合原料，調節聚合溫度進行聚合。 此時之聚合溫度爲1 5(TC，又且將反應槽之攪拌旋轉 數調整爲1 50 rpm。繼續聚合，從反應槽連續地汲出 聚合液供給至脫除揮發分裝置後，經由擠壓機而得到 苯乙烯聚合物（4)。 【合成例5】 使用由容量爲1 5升之柱塞流式塔型反應槽（「新 聚合物製造程序方法」（工業調查會，佐伯康治/尾見 信三著）185頁，第7.5(b)圖）所記載之三井東壓型同 種類的反應槽，並顯示分隔成1 〇段C 1 / C 0 = 〇 . 9 5 5之 物）與2座1 〇升之完全混合槽直列地接續而成之連續 -29 - 200415093 聚合裝置，以製造熱可塑性樹脂。柱塞流式塔型反應 槽係構成粒子形成製程，第2反應槽之第1座的完全 混合槽係構成粒子徑調整製程，而第3反應槽係構成 後聚合製程。 在前述柱塞流式塔型反應槽中調整由2 2重量份之 丙烯腈、25重量份之乙基苯、13重量份之苯乙烯-丁 二烯橡膠（日本*#^'股份有限公司製S310S)、0.2重量 份之t-月桂基硫醇、〇.〇5重量份之丁基過 氧）3,3,5-三甲基環己烷所構成之原料，將此種原料以 1 〇公斤/小時連續地供給至3段之攪拌式聚合槽列反 應器中，以進行單體體之聚合。又，第1之柱塞流式 塔型反應槽係設定爲8 8 t、第2反應槽設定爲1 2 5。(：、 而第3反應槽設定爲140 °C。將來自第3反應槽之聚 合液供給至由預熱器（21 0〜250 °C )和減壓室（40 To rr)形 成之脫除揮發分裝置後，經由擠壓機而得到分散有橡 膠粒子之熱可塑性樹脂（5)。所得到的橡膠分散相之重 量平均粒徑爲0.5微米。 【實施例1〜5、比較例1〜4】 將在合成例1〜5所得到的樹脂、和下述之靜電防 止劑依照表彳所不之ί爹混比例混合，使用附有出口之 40毫米雙軸擠壓（日本製鋼所股份有限公司製「TEX-44 」）’ 於 2 0 0 °C 溶融混 煉並切 斷而得 到九粒 。也 就是 說，本九粒係實施1次之脫除揮發分處理。此處所使 -30- 200415093 用的靜電防止劑係爲三洋化成工業股份有限公司製「卜 雷斯塔特NC6321」（聚醚酯醯胺，折射率爲1.516)及 月桂醯基苯并磺酸鈉。依照下述之方法測定所得到的 九粒之熔融流速、灰分及4-乙烯基環己烯含量。將測 定結果示於表1。 使用所得到的九粒，並使用日本製鋼所股份有限 公司製 J450E-C5之射出成形機，以200°C之樹脂溫 度、模具溫度爲50 °C、射出速度爲45毫米/秒、射出 壓力爲1 600公斤/平方公分進行射出成形，製做成如 第1圖所示之容器。實施例1〜5及比較例1〜4分別可 以得到外觀良好之成形品。但是在實施例4及5中因 爲白濁而難以視認內部。又，依照下述之方法進行臭 氣之官能評價。將評價結果示於表2。 (1 )熔融流速 以ASTM D-1 238爲基準，測定熔融流速（克/10分 鐘）。測定溫度爲2 2 0 °C，荷重爲1 〇公斤。 (2) 灰分 在白金坩堝中正確地量取所測定之乾燥重量爲約 1〇克之九粒試料，並在設置於通風室內之電氣錐型爐 上化後，將溫度設定在8 0 0 °C之電氣爐內的白金坩堝 予以移出並放置4小時，然後取出白金坩堝於乾燥劑 中放冷後量稱其重量，從該重量差算出灰分（％ ) ° (3) 4 -乙烯基環己烯含量 -3 1 - 200415093 將試料之九粒溶解於二甲基甲醯胺中，使用附有 火焰離子檢測器（F I D )之哈維特帕克得公司製5 8 9 0 Π型 氣體色譜分析儀，分析試料溶液中之4 -乙烯基環己烯 含量。定量時使用已知濃度的4-乙烯基環己烯含量的 二甲基甲醯胺溶液製做之檢量線。 (4) 全光線穿透率 使用爲3毫米之試驗片，利用村上色彩技術硏究 所股份有限公司製之反射•折射率計H R -1 0 0測定之。 (5) 霧値 使用和全光線穿透率測定相同的試驗片，利用村 上色彩技術硏究所股份有限公司製之反射•折射率計 H R -1 0 0進行測定。 (6) 以AST M D-2 56爲基準，測定凹口附帶艾佐得 (Izod)衝擊強度（Mpa)。 (7) 靜電防止性 使用爲3毫米之試驗片，於2 3 °C、5 0 % R Η之溼度 下狀態調整1個月，利用東亞電子工業股份有限公司 製之超歐姆測定儀SN8210測定水洗處理前後之表面 固有電阻値（Ω )。 (8) 臭氣官能評價 將以射出成形所得到的容器常溫放置於開放空間 歷2 4小時，上盒子與下盒子嵌合密封於常溫下放置1 小時。然後，藉由5名臭覺敏感的測試人員嗅聞打開 -32- 200415093 上盒子後之臭氣程度來進行臭氣官能評價。依照以下 之基準進行評點。 5點：臭味明顯且強烈； 4點：感覺相當的臭； 3點：感覺臭味； 2點：感覺稍微的臭； 1點：不感覺臭。200415093 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a container for a clean room. In more detail, the present invention relates to a masterbatch resin composed of an aromatic vinyl monomer and other copolymerizable monomers. Thermoplastic resin composed of olefinic rubber particles, the ash content of the thermoplastic resin is 0. 2% by weight or less clean room container. [Previous technology] In order to prevent the contamination of silicon wafers in the semiconductor manufacturing process, glass substrates in the manufacturing process of liquid crystal panels, and metal discs in the manufacturing process of hard disks', they are cleaned by a clean room. In these manufacturing procedures, various containers are used in order to enable efficient handling of these substrates. For example, 'there are multiple substrates that can be accommodated at the same time and transferred from a specific process in the clean room to the next process. Case of container 'There are also cases where various treatments are carried out in situ in a container. There are various resins used as the material of the container depending on their purpose. For example, although polypropylene is inexpensive, it cannot be used for applications that require transparency, dimensional accuracy during molding, and rigidity. Although polyresidues are transparent and have excellent impact resistance, it is difficult to prevent static electricity in the original state, and it is difficult to make the resin expensive. In addition, acrylonitrile-styrene copolymer (ABS resin) and methacrylic acid are 6 $: Although the resin is transparent, the MS resin is 200415093. In addition to the poor impact resistance, it is easy to slip due to sliding It is abraded by rubbing, especially it is difficult to use it in the polluted clean room. In addition, polybutylene terephthalate (PBT) and polyetheretherketone (PEEK) have good heat resistance ', but are opaque and have high resin costs. Acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) and resins similar to them are excellent in the balance of dimensional accuracy during molding, smoothness, rigidity, and impact resistance of the surface of the molded product, and A general-purpose resin with relatively low resin cost. As described below, it is also possible to provide permanent antistatic properties and handling properties. For example, 'Japanese Patent Application Laid-Open No. 9-9271 4 has a static-proof container for accommodating semiconductor wafers. Examples of this publication describe an example of an ABS-based permanent static prevention resin 'which is molded at a temperature of 230 to 240 ° C (Examples 1, 3, and 4). The container systems described in the examples have good antistatic properties and are excellent in transparency depending on the product (Example 3). Japanese Unexamined Patent Publication No. 62-1 1 9256 describes a copolymer mixture composed of a (meth) acrylate monomer and other copolymerizable vinyl monomers in the presence of a rubber polymer. A thermoplastic resin composition in which a polymer obtained by branch polymerization is blended with polyetheresteramide. It is also described that this resin composition is excellent in permanent static prevention, impact resistance, and transparency, and can be used to prevent obstacles caused by static electricity. For example, 200415093 can be used in an I c carrier container. . Also, Japanese Patent Application Laid-Open No. 9-59462 describes that any one of the residual styrene-based monomer and the residual 4-vinylcyclohexene is less than a certain amount, and the average particle diameter and distribution of the rubber particles are constant. Range of ABS resin composition. By using these resin compositions, a odorless product having excellent impact strength and tensile strength and excellent gloss can be produced. This publication also describes that AB S resin can be used in housings for home appliances and molded vehicles. According to Japanese Unexamined Patent Publication No. 9-9271 4 and Japanese Unexamined Patent Publication No. 62-1 1 9256, an antistatic container for semiconductor wafer storage made of ABS resin is known. However, as the resin used in the clean room container, ABS and similar resins are practically unused. One of the most common reasons is the problem of the pollution source described below. In the case of containers used in clean rooms, most of the stored items are extremely repellent to pollution, so it is important that the containers cannot be their source of pollution. Of particular concern among pollutants is the pollution caused by metal ions. For example, as far as the semiconductor manufacturing process is concerned, during the diffusion operation, the impurities of the metal ions may diffuse into the circuit and increase the defect rate. Furthermore, it is necessary to simultaneously prevent contamination by organic substances other than metal ions. However, a representative method for manufacturing AB S resin is a 200415093 process including graft modification of diene rubber particles obtained by emulsion polymerization in an emulsion. In order for the polymerization reaction in the emulsion to proceed smoothly, it is necessary to have a large amount of an emulsifier, which in most cases is a surfactant composed of a metal salt. In addition, the obtained grafted rubber particles need to be separated from the emulsion to be coagulated. However, in this case, salting out is most likely to occur. In this case, the coagulated material will further contain a large amount of salt. As a result, most of the commercially available A B S resins have a considerable amount of metal salt components remaining. Therefore, it is far away from substances that have the potential to become a source of pollution, so that nowadays, A B S and similar resins are rarely used as materials for clean room containers. Also, although Japanese Unexamined Patent Publication No. 9-59462 describes an ABS resin with a small amount of residual organic matter, it has a problem of odor when it is made into a housing of a home appliance and a molded article of a vehicle, let alone a source of pollution in a clean room The problem. The present invention is to solve the above-mentioned problems, and to provide a clean room container made of ABS and a similar thermoplastic resin, which has a low ash content and a low possibility of contamination by metal ions. purpose. A container for a clean room, which is a diene polymer made by polymerizing a diene monomer as a main component in a master batch resin composed of an aromatic vinyl monomer and other copolymerizable monomers. A thermoplastic resin composed of rubber particles is formed, and the ash content of the thermoplastic resin is 0.2% by weight or less. -9- 200415093 A container suitable for storing a plate-like body selected from a semiconductor substrate, a display device substrate, and a recording medium substrate. Thereby, a container for a clean room, which is formed of A B S and its similar resins, but has at least an ash content that is difficult to become a source of metal pollution, is provided. [Summary of the Invention] The above-mentioned problem can be solved by providing a master batch resin composed of an aromatic vinyl monomer and other monomers copolymerizable with a diene monomer as a main component for polymerization. The thermoplastic resin composed of the diene rubber particles is formed, and the ash content of the thermoplastic resin is 0. 2% by weight or less for clean room containers. In this case, it is desirable that at least one of the aforementioned copolymerizable other monomers is appropriately selected from vinyl cyanide monomers and unsaturated carboxylic acid alkyl ester monomers. The thermoplastic resin is preferably a diene rubber of 5 to 50% by weight and 10 to 90% by weight. /. Aromatic diene monomer and 10 ~ 90 weight. /. The aforementioned copolymerizable other monomers are polymerized. The embodiment of the thermoplastic resin described above is an emulsion in which diene rubber particles obtained by polymerizing a diene and a diene monomer are dispersed, and an aromatic vinyl monomer and other copolymerizable ones are used. A graft resin obtained by copolymerizing monomers and a resin obtained by copolymerizing another aromatic vinyl monomer and another copolymerizable monomer are melt-mixed. In this case, the graft copolymerized resin particles are solidified with a small amount of acid, washed, and then supplied to the melt-mixing ratio -10- 200415093. Also, the thermoplastic resin is a diene rubber obtained by polymerizing a diene monomer and dissolving it in an aromatic vinyl monomer and other copolymerizable monomers, and then making the aforementioned aromatic vinyl monomer It is also an ideal embodiment to polymerize the polymer and other monomers copolymerizable therewith. The diene monomer is desirably 1,3-butadiene, and the 4-vinylcyclohexene content of the thermoplastic resin is 100 ppm or less. The thermoplastic resin preferably contains an antistatic agent made of polyetheresteramide or an antistatic agent made of conductive carbon. Ideally, after the sample cut from the molded product is held at 150 for 10 minutes, the amount of organic gas generated within 10 minutes in terms of styrene is 600 ppm or less. Ideally, the thermoplastic resin is a resin having a haze of 20% or less when it is formed into an injection molded product having a thickness of 3 mm. In addition, ideally, it is a product obtained by setting the roller set temperature at the time of injection molding below 220 ° C and then injection molding. A preferred embodiment of the present invention is the above-mentioned clean room container for housing a plate-shaped body selected from a semiconductor substrate, a display device substrate, and a recording medium substrate. [Embodiment] Hereinafter, the present invention will be described in detail. The container for clean room of the present invention is a masterbatch resin composed of an aromatic vinyl monomer and other copolymerizable monomers. 200415093 disperses two dimer monomers polymerized by a diene monomer. A thermoplastic resin made of olefinic rubber particles. The thermoplastic resin used in the present invention is a copolymer formed of an aromatic vinyl monomer 'and other copolymerizable monomers. It is not a polymer composed only of aromatic vinyl monomers. By forming a copolymer with other monomers, it can be easily made into excellent impact resistance, transparency, heat resistance, and chemical resistance. Of resin. The polymers are usually a random copolymer. The aromatic vinyl monomer used here is, for example, styrene, methylbenzene, p-toluene, etc. One or two or more of these can be used. The copolymerizable other monomer is not particularly limited as long as it can be copolymerized with an aromatic vinyl monomer. For example, it may be acrylonitrile, methacrylonitrile, or the like Aminated vinyl monomers represented by acrylates, and unsaturated (meth) acrylates represented by methacrylates, ethylacrylates, methmethacrylates, ethylmethacrylates, etc. Residual acid ester monomers, unsaturated carboxylic acid or unsaturated dicarboxylic anhydride monomers such as acrylic acid, methyl propionic acid, maleic acid, maleic anhydride, citraconic anhydride, maleic acid, methyl maleic acid Maleimide-based monomers such as amidine, ethylmaleimide, N-phenylmaleimide, and 0-chloro-N-phenylmaleamate. These other copolymerizable monomers may be used singly or in combination of two or more kinds. However, among these, the aforementioned other copolymerizable monomers, 200415093, are preferably one or more selected from aminated ethylene monomers and unsaturated carboxylic acid alkyl ester monomers. Copolymerization with aminated ethylene monomers improves the stability, chemical resistance, rigidity, and dimensional stability. Further, by copolymerizing with an unsaturated carboxylic acid alkyl ester monomer, transparency, hardness, and rigidity are improved. It is preferable to copolymerize these two together. The thermoplastic resin used in the present invention is a product in which diene-based rubber particles obtained by polymerizing a diene monomer are dispersed in the master batch resin. At this time, the proportion of the diene monomer in the rubber particles is more preferably 50% by weight or more, and more preferably 80% by weight or more. It is used as a diene monomer. For example, it may be 1,3-butadiene, isopropylene, or the like, and one or two or more of them may be used. However, among these, 1,3-butadiene, which is excellent in performance and low in cost, is ideally used. Specific polymers, for example, polybutadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), polyisopropylene rubber, etc., especially polybutadiene Rubber is an excellent resin that can improve low-temperature impact resistance, etc., and it is also ideal for low cost. As far as the average particle diameter of the above rubber particles is concerned, although it is not particularly limited, it is preferably 0. 〇5 ~ 10 microns, more preferably 〇8 ~ 5 microns. The composition ratio of the thermoplastic resin used in the present invention is not particularly limited, but it is preferably a diene rubber of 5 to 50% by weight and 10 to 90% by weight. /. An aromatic diene monomer and 10 to 90% by weight of the aforementioned copolymerizable other monomers are polymerized to form -13-200415093. Such a composition ratio indicates the ratio of each component in the thermoplastic resin in the final molded product. For example, the diene is preliminarily mixed with a predetermined amount of an aromatic diene monomer and other copolymerizable monomers After the rubber is modified, when it is further melted with a copolymer composed of another polymerized aromatic monomer and copolymerizable other monomers, the ratio is the proportion of the total amount of the mixture. The content of the diene rubber is preferably 5 to 50 weight. /. . When the content is less than 5% by weight, the impact resistance may be insufficient. Therefore, it is preferably 10% by weight or more. On the contrary, if it exceeds 50% by weight, the rigidity or formability may be lowered. Therefore, it is preferably 30% by weight or less, and more preferably 20% by weight or less. In addition, the content of the aromatic vinyl monomer-derived component is more preferably in the range of ≧ 0 to 90% by weight. When less than 10 weight. /. In this case, the rigidity or formability is likely to decrease, so it is more preferably 20% by weight or more. When it exceeds 90% by weight, the impact resistance may be lowered, but it is preferably 80% by weight or less. In particular, when transparency is required, it is preferably 50 weight. /. In the following, it is more preferably 30 weight. /. the following. The content of other copolymerizable monomer-derived components is preferably from 10 to 90 weight. /. . More ideal is at 20 weight. /. It is more than 80% by weight. In particular, in the case where transparency is particularly required, other monomers which can be copolymerized preferably contain an unsaturated carboxylic acid alkyl ester monomer-derived component, and the content thereof is more preferably 40 to 80 weight. /. . In this way, the refractive index difference between the master batch resin and the rubber particles can be made smaller by -14-200415093, and the entire resin can be made transparent. The method for producing the thermoplastic resin used in the present invention is not particularly limited, and it can be produced by a polymerization method using emulsion polymerization, suspension polymerization, block polymerization, solution polymerization, or a combination thereof. However, among these, for the diene rubber, although it is a process of graft copolymerization containing an aromatic vinyl monomer and other copolymerizable monomers, the dispersion of rubber particles, From the viewpoint of the strength of the interface between the rubber particles and the master batch resin, 0 is preferred. When the diene rubber is modified, it may be graft-modified in an emulsion (latex) containing rubber, or may be graft-modified in a solution in which rubber is dissolved. One of the ideal manufacturing methods is to copolymerize an aromatic vinyl monomer and other copolymerizable monomers in an emulsion in which diene rubber particles obtained by polymerizing a diene monomer are dispersed. A method in which the formed graft copolymerization resin, another aromatic vinyl monomer, and other copolymerizable monomers are copolymerized and melt-mixed together. When graft copolymerization is performed in an emulsion, the rubber composition, particle size, and sol content can be easily controlled, and a high-performance resin excellent in transparency, impact resistance, and moldability can also be easily obtained. In addition, the graft copolymerized resin particles synthesized in the emulsion are diluted with another block (or solution) polymerized copolymer to dilute the metal salt component of the emulsion source. -15- 200415093 As for the above manufacturing method, although various additives such as emulsifiers, polymerization initiators, salting-out agents can be used in the emulsion polymerization process, most of these are metal salts, which will have Easy to mix into the final product. In the emulsion polymerization, it is necessary to use an amount equivalent to that of the emulsifier. However, most of them are alkali metal salts of higher fatty acids and alkali metal salts of sulfuric acid. In addition, as a polymerization initiator in the emulsion polymerization, although a peroxide or the like can be used, there are also latex-based initiators using an organic hydrogen peroxide. In this case, an iron salt or the like is mostly used. Furthermore, when the obtained graft copolymerized resin particles are solidified after the emulsion polymerization, the alkali metal salt and alkaline earth metal salt are added in a high concentration and then precipitated. Therefore, in order to reduce the content of metal ions in the final product, that is, ash, in the solidification process after the above-mentioned emulsion polymerization, it is more preferable to use an acid to solidify the acid. For example, it may be hydrochloric acid And sulfuric acid. At this time, it does not matter if auxiliary salts are used, but it is more preferable not to use salts, but to solidify them with acid only. In this way, metal salts can be avoided from being mixed in the solidification process. In addition, for the washing conditions after coagulation, it is preferable not only to increase the amount of washing water but also to increase the number of washing times. In particular, the washing water should be at least the same volume as the apparent volume of the graft copolymerized resin particles to be washed, more preferably 2 times or more, and more preferably 3 times or more. It is more preferable to perform the washing-dehydration step twice or more, and it is more preferable to repeat the washing three times or more. In the general ABS resin manufacturing process, from the viewpoint of economics, the washing-dehydrating process is usually -16- 200415093 without repeated operations. As described above, the graft polymerized resin particles after the emulsion polymerization are solidified with a small amount of acid, and sufficiently washed, and then melt-mixed with another block (or solution) polymerized copolymer, thereby making it possible to Effectively reduce ash. The method of melt-mixing is not particularly limited, and it can be mixed by using a known kneading device such as an extruder, a Bentley mixer, a roll, and a kneader. In this case, it may be mixed with other components such as an antistatic agent at the same time. 0 One of the other ideal manufacturing methods is to dissolve a diene rubber polymerized from a diene monomer in an aromatic vinyl monomer and other copolymerizable monomers, and then make the aforementioned aromatic A method for polymerizing a group ethylene monomer and other monomers copolymerizable therewith. In this case, 'a block polymerization method of polymerization in a state where no other solvent is contained may be used, or a solution polymerization method of polymerization in the presence of another solvent, such as ethylbenzene, may be used, and any one may be used. · According to these methods, the thermoplastic resin used in the present invention can be produced without going through the emulsification polymerization process, and the residual amount of the metal salt from the emulsifier and the salting-out agent can be reduced. Such a manufacturing method is difficult to control the particle size and composition of rubber particles, and therefore, in comparison with a manufacturing method having an emulsion polymerization process, transparency and impact resistance are insufficient in most cases. It must not be a widely implemented manufacturing method. However, since it can reduce the amount of residual metal salts, it is a better method for the use of the present invention. The ash content of the thermoplastic resin used in the present invention is 0.2% by weight or less. When the ash content exceeds 2% by weight, metal ions in the clean room are likely to be a source of contamination, which is not suitable. For example, in a semiconductor manufacturing process, as long as it is a container directly in contact with a wafer such as a wafer carrier, it may become a direct source of contamination of the wafer, and there may be a case where metal ions are dissolved in the treated water. In addition, even in a case where the carrier contains a carrier so that the container does not come into direct contact with the wafer, the abraded dust also adheres to the wafer or the carrier and has an adverse effect. In particular, with regard to semiconductor manufacturing processes, when the metal ions are impure during the process of diffusing a substance by heating, it is likely that the metal ions will diffuse into the circuit and the defective rate will increase. The thermoplastic resin preferably has an ash content of 0. 18% by weight or less, more preferably 0-15% by weight. In addition, as for the thermoplastic resin used in the present invention, the diene monomer used therein is preferably 1,3-butadiene, which has been as described above. In this case, the 4-vinylcyclohexene content of the thermoplastic resin is preferably 100 ppm or less. 4-Ethylenecyclohexene is a cyclic dimer of 1,3-butadiene because it is a by-product mainly during the polymerization of a diene monomer. It has an unpleasant odor and is an undesired substance. This odor is particularly problematic when working in a closed space such as a clean room. Also, in a closed space such as a clean room, volatile organic compounds are prone to stay, so they are a source of pollution and therefore are not an ideal substance. The content of 4-ethylene ring 200415093 is preferably less than 80 p p m, and more preferably less than 60 p p m. In the case of emulsification polymerization, in order to reduce the content of 1,3-butadiene, it is more preferable to heat the emulsion after emulsification polymerization to volatilize and remove unreacted diene monomers and volatilize and remove byproducts 4 -The second ring is thin. The heating method ideally uses steam distillation, preferably at a temperature of 60 ° C or more, more preferably at a temperature of 70 ° C or more, preferably at least 10 minutes, and more preferably at least 30 minutes. Steam distillation φ operation. Further, it is more preferable to strengthen the washing conditions after solidification after the emulsion polymerization. In this case, the preferable washing conditions are as described above. In addition, in the case of bulk polymerization or solution polymerization, it is more preferable to reduce the content of 4-Ethylcyclopentane by strengthening the process of removing volatiles. Specifically, after the polymer is finished, it is preferable to reduce the pressure to 180 ° C or higher, more preferably 200 ° C or higher, and reduce the pressure to 100 To rr or less, ideally 50 Torr or less, to remove unreacted Monomer, etc., and simultaneously remove 4-vinylcyclohexene. When a solvent is used in the polymerization, although the solvent and 4-vinylcyclohexene are removed at the same time, it is preferable to remove 4-vinylcyclohexene with good efficiency. The thermoplastic resin used in the present invention may contain various additives. In the description of the present invention, the so-called thermoplastic resin includes a composition containing an additive. Among various additives, for example, it contains an antistatic agent because it can prevent the electrostatic destruction of semiconductor wafers and from the viewpoint of preventing the adhesion of fine particles. -19- 200415093 is preferable. Such antistatic agents may be, for example, cationic surfactants such as alkylamines, sulfates of higher alcohols, sulfate esters of ethylene oxide adducts of higher alcohols, and ethylene oxide additions of alkylphenols. Sulfuric acid ester salt, alkane sulfonate, alkyl benzo sulfonate, alkyl sulfosuccinate salt, salt of furone polycondensate of naphthalenesulfonic acid, ethylene oxide adduct of higher alcohol Anionic surfactants such as silicate salts, silicate salts of ethylene oxide adducts of alkylphenols, silicate salts of ethylene oxide adducts of alkylphenols, sorbitol esters of higher fatty acids, higher fatty acids Monoglyceryl ether ester, Monoglyceryl ether ethylene oxide adduct of higher fatty acid, Ethylene oxide adduct of higher alcohol, Ethylene oxide adduct of higher fatty acid, Ethylene oxide adduct of higher alcohol, Ammonium ethylene oxide Non-ionic surfactants such as adducts, ethylene oxide adducts of alkylamines, polyalkylene glycols, polyalkylene glycol-based copolymers, polyetheresteramines, conductive carbon, and the like. One or more of these may be used. Among these, it is more preferable to use polyetheresteramide. Because polyetheresteramide does not form salts, there is no need to worry about dissolving the salts. Furthermore, the molecular weight is relatively high, and the compatibility with the thermoplastic resin used in the present invention is also good, so that it does not bleed out, so that the effect of preventing static electricity can be exhibited for a long period of time. Specific examples of the polyetheresteramide include, for example, carbon atoms obtained from an aminocarboxylic acid having 6 or more carbon atoms, a lactone having 6 or more carbon atoms, and a diamine and a dicarboxylic acid Polyammonium compounds (A1) selected from at least one of the salts of 6 or more and polyamines (A) and polyoxyethylenes derived from carboxyl groups at both ends derived from -20-200415093 dicarboxylic acid (A2) A compound obtained by polycondensing a polyether diol (B) formed from an alkylene glycol and / or a biphenyl ester ethylene oxide adduct. Furthermore, in the case where transparency is required, it is desirable that the polyetheresteramide is processed to have the same refractive index as that of the thermoplastic resin used in the present invention. The refractive index of polybutadiene is 1. 52, because the refractive index of the masterbatch resin is treated to be the same as the refractive index when transparency is required, the refractive index of polyetheresteramide is preferably 1 at room temperature. 48 ~ 1. 56, more preferably 1. 50 ~ 1_54, the most appropriate is 1. 51 ~ 1. 53. If the application is not required to be transparent, it is preferable to use conductive carbon as an antistatic agent. As will be described later, when an organic compound is used as an antistatic agent, it goes without saying that there is of course a fear of thermal decomposition during molding.楣 In this regard, conductive carbon such as graphite powder, carbon black, carbon fiber, and carbon nanotubes is hardly decomposed at the temperature at which the thermoplastic resin is melt-molded. Therefore, it is also desirable to use conductive carbon particles as an antistatic agent in applications such as a container for a clean room that are likely to be polluted by volatile organic compounds. In addition, although the use ratio of the above-mentioned antistatic agent is not particularly limited, it is preferably based on the physical property balance surface, and the thermoplastic resin of the present invention preferably contains 1 to 30 weight. /. . Moreover, the thermoplastic resin used in the present invention may be added with a known additive within a range that does not impair the effect of the present invention. For example, an oxidation inhibitor, an ultraviolet absorber, and -21-200415093 smoothing agent may be added as necessary. , Colorants, tinctures, etc. However, the so-called difficult to generate pollutants, when considering the performance required for the clean room container of the present invention, it is better to keep the amount of such additives to a minimum. The mixing method is not particularly limited, and an extruder, a Berry Mixer, a roll, a kneader, or the like may be used, and a mixing method may be used. As described above, when the graft copolymerized resin particles and another copolymerized resin are melt-mixed, in order to simultaneously remove the volatile components during melt-mixing, it is desirable to perform volatile removal deal with. A method for removing the volatilization fraction is, for example, the most appropriate method for reducing the pressure in a molten state. Specifically, melt-kneading is preferably performed using an extruder having a reduced-pressure outlet. The extruder can be a uniaxial extruder or a biaxial extruder. Further, the outlets may be provided not only at one position but also at a plurality of positions. At this time, the ideal melt-kneading temperature is 1 60 to 220 ° c. In addition, by repeatedly performing such a volatile-removing treatment, the content of volatile components in the resin can be further reduced. For example, if an extruder having a pressure-reducing outlet is used for melt-kneading, it is more preferable to repeatedly melt-knead the plate-like material to be melt-kneaded again. Although the melt flow rate (220 t, 10 kg load) of the thermoplastic resin used in the present invention is not particularly limited, it is usually 1 to 100 g / 10 minutes. From the viewpoint of formability, it is more preferably 5 -22- 200415093 g / 10 minutes or more, and from the viewpoint of strength, it is more preferably 50 g / 10 minutes or less. In the case where the present invention is used for applications requiring internal visibility, the thermoplastic resin is preferably a transparent material. This is the case, for example, when using a cassette with a silicon wafer carrier inside. In this case, the thermoplastic resin is more preferably a resin having a fog of less than 20% when injection-molded to a thickness of 3 mm. By having a fog of less than 20%, not only the inside of the container can be easily seen from the outside, but also the appearance is beautiful. In addition, for example, a reading device can be used to read a silicon wafer attached to a carrier from the outside for production management. In addition, if the total light transmittance is expressed, it is more preferably 70% or more, and more preferably 80% or more. By using the thermoplastic resin obtained in this way, a container for clean room of the present invention is formed. The molding method is not particularly limited, and various melt molding methods such as injection molding, extrusion molding, and melt blow molding can be used. Further, a secondary processing such as thermoforming may be performed on a sheet or the like which has been extruded once. Among these, for example, a container for a clean room requires a relatively complicated dimensional accuracy. Therefore, it is preferable to perform injection molding. The molding conditions at the time of injection molding are also not particularly limited. However, it is preferable to mold the rollers at a set temperature of 220 ° C or lower. In general, when ABS resin is injection-molded, it is mostly injection-molded at a resin temperature of 230 ° C or higher. However, in the present invention, it is expected that the decomposition of the resin is suppressed by 2 2 0 -23- 200415093 ° c. To a minimum. The melting time of the injection molding resin is usually not as long as possible. 'For general use, considering the moldability and molding speed, it is better to mold at a high temperature; for the purpose of cleaning indoor use,' not only can reduce the cause The amount of organic matter that occurs during thermal decomposition during melting is important. Therefore, it is preferable to lower the possible forming temperature to the lowest forming temperature. The possible forming temperature varies depending on the composition of the resin and the melt flow rate, and is set in consideration of these factors. For example, by increasing the proportion of the components derived from the unsaturated carboxylic acid alkyl ester monomer in the resin, it is possible to easily form at a relatively low temperature. The set temperature of the drum during injection molding is preferably below 210 ° C, and more preferably below 200 ° C. Moreover, it is usually above 160 ° C. In addition, the temperature of the molten resin during injection molding also affects the thermal decomposition behavior of additives blended in the resin. For example, the thermoplastic resin used in the clean room container of the present invention preferably contains an antistatic agent. Among them, polyetheresteramide is more preferable as described above. In the case of melt molding, although the amount is small, such an antistatic agent is thermally decomposed. At this time, in the case of high-temperature molding, the amount of low-molecular-weight amines and amidines (including lactones) due to thermal decomposition will increase. Amines and amidines are dissolved in water and permeate the processing liquid, which easily contaminates semiconductor wafers. Furthermore, compounds containing such nitrogen elements may cause alkalinity such as ammonia and amines in semiconductor manufacturing processes such as thermal diffusion processes Because of matter, it is a more objectionable source of pollution than ordinary organic compounds composed of carbon, -24-200415093 hydrogen, and oxygen. Therefore, 'especially when using an antistatic agent containing such a nitrogen element', it is preferable to form it at a low temperature as much as possible. The amount of decomposed organic matter contained in the clean room container of the present invention formed in this manner is preferably as small as possible. Specifically, it is more preferable that the sample cut from the molded product be held at 150 ° C for 10 minutes, and the styrene conversion 量 of the amount of organic gas generated within 10 minutes is preferably 600 ppm or less. It is more preferable to be 400 ppm or less', and even more preferable to be 300 p p m or less. When the amount of the decomposed organic matter is reduced to such a level, the volatile components can be effectively reduced when the resin as described above is manufactured, and at the same time, the molding can be performed as effectively as possible at a low temperature. The container for clean room in the present invention is a container that can be used in clean room. It is a container for storing raw materials, intermediate products or products, and it is not particularly limited. For example, it is a container for storing an ideal article such as a semiconductor substrate, a display device substrate, and a plate-like body selected from a recording medium substrate. Examples of the semiconductor substrate include a substrate for manufacturing integrated circuits and a substrate for manufacturing solar cells. This material is not particularly limited to those represented by silicon. The shape may be a circle such as a silicon wafer or a square shape such as a solar cell. It does not matter if the silicon wafer is circularly cut into wafers. One of the representative embodiments is a container for silicon wafers. In the past -25- 200415093, silicon wafers have gradually become large-caliber, so the size of the containers for silicon wafers has gradually increased. Therefore, it is possible to maintain the shape of a large-sized container without damaging it, and it is desirable to use a resin having excellent rigidity and impact resistance. From this viewpoint, the clean room container of the present invention is most preferable. In addition, as the size becomes larger, the level of dimensional accuracy required for the entire molded article becomes stricter, so the container for clean room of the present invention which can be formed with good dimensional accuracy is most desirable. Therefore, the clean room container of the present invention is ideally used for silicon wafers of 6 inches or more, is more preferably used for silicon wafers of 8 inches or more, and is more preferably used for silicon wafers of 300 mm or more. In this case, in the case of a container called a carrier where a silicon wafer is directly arranged, because the silicon wafer is in direct contact with the carrier, metal contamination is particularly likely to be a problem, and staggered contamination is likely to occur through a processing liquid or the like. Therefore, a container for a clean room according to the present invention is more suitable for such a carrier. In this case, it is particularly preferable to use a transparent resin that can visually recognize the inside. In addition, since the volatile component is easily filled in the case, it is preferable that the volatile component is the least contaminated by the volatile component. For this reason, even for a container that is formed as a single body of a carrier and a box, the container for clean room of the present invention is most preferably used. Examples of the display device substrate include, for example, a substrate for manufacturing a liquid crystal display device, a substrate for manufacturing a plasma display device, and a substrate for manufacturing an electroluminescent display device. The typical material of these substrates is glass, and other articles such as transparent resins do not matter. In the case of -26-200415093 nt ® display device substrate, since there is a circuit for pixel driving 'which is contaminated by metal, it is ideal to use the clean room container of the present invention. Since the display device substrate is mostly extra large, it is preferable to use the clean room container of the present invention similarly to the aforementioned large-diameter silicon wafer. Also, a recording medium substrate is, for example, a hard disk substrate and an optical disk substrate. In the case of a hard disk substrate, materials such as metal and glass are used, but they are not particularly limited. In the case of an optical disc substrate, the use of a transparent plastic representing polycarbonate is used as a representative, but it is not particularly limited. With regard to these recording media, although the composition of the recording film differs according to its recording form, since the recording density has increased dramatically in recent years, even a small amount of pollutants can affect performance, so the use of the present invention The container is ideal. [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in more detail using examples. [Synthesis Example 1] In a polymerization reactor substituted with nitrogen, put 50 parts (solid matter) of polybutadiene latex (weight average particle diameter of 0. 3 //, sol content is 85%), 0. 1 part of ethylene diamine tetraacetic acid, 0. 〇 〇 1 iron sulfate, 〇. 3 parts of sodium formaldehyde sulfonate were heated to 60 ° C, and then continuously added from 3 parts of acrylonitrile, 12 parts of styrene, 35 parts of methyl methacrylate and 0. A mixture of 2 parts of cumene hydrogen peroxide-27- 200415093 was polymerized at 60 ° C to obtain a graft copolymer emulsion emulsion. Then, using the latex relative to 100 parts by weight (solid matter) as 0. After salting out 3 parts by weight of magnesium sulfate, add 1% of the graft copolymerized resin particles. 5 times the volume of water was stirred, dehydrated, washed, and then dried to obtain graft copolymerized resin particles (1). [Synthesis Example 2] Graft copolymerized resin particles were obtained in the same manner as in Synthesis Example 1 except that the point of performing steam distillation after polymerization in Synthesis Example 1 and the coagulation and washing processes were changed. That is, steam was blown into the graft copolymerized latex obtained after the polymerization, and steam distillation was performed for 1 hour. The temperature of the latex at this time was 80 ° C. After steam distillation, coagulation was performed using 0.1 parts by weight as a coagulant, and 2. After 5 times the volume of water was stirred, the dehydration washing operation was repeated 3 times. Except for the above point, the same procedures as in Synthesis Example 1 were performed to obtain graft copolymerized resin particles (2). [Synthesis Example 3] In a polymerization reactor substituted with nitrogen, put 130 parts of pure water and 0. After 3 parts of potassium persulfate, the temperature was raised to 65 ° C with stirring. After that, 10 parts of acrylonitrile, 30 parts of styrene, 60 parts of methyl methacrylate and 0. 35 parts of mixed monomer consisting of t-lauryl mercaptan, and 30 parts of an emulsifier aqueous solution containing 2 parts of -28-200415093 heterogeneous potassium rosinate. Then, the polymerization system was heated to 70 ° C and aged for 2 hours to obtain a styrenic polymer latex. Then, the amount of latex relative to 100 parts by weight (solid matter) is 2. After 5 parts by weight of magnesium sulfate was salted out, 1. 5 times the volume of water was stirred, dehydrated, washed, and then dried to obtain a styrene polymer (3). [Synthesis Example 4] A continuous polymerization device formed by using a completely mixed reaction tank with a capacity of 20 liters, and continuously supplying 30 parts of styrene and 70 parts by using a plunger pump at 13 kg / hour. Methyl methacrylate, 10 parts by weight ethylbenzene, 0.1 05 parts by weight of t-lauryl mercaptan, and 0. 015 parts by weight of a polymerization raw material composed of butyl peroxy (2-ethyl hexane ester) as a polymerization initiator is adjusted by polymerization at a polymerization temperature. The polymerization temperature at this time was 15 ° C, and the number of stirring rotations of the reaction tank was adjusted to 150 rpm. The polymerization was continued, and the polymerization solution was continuously drawn from the reaction tank to the volatile-removing device, and then passed through an extruder Then, a styrene polymer (4) was obtained. [Synthesis Example 5] A plunger-flow tower type reaction tank having a capacity of 15 liters ("New Polymer Manufacturing Procedure Method" (Industrial Survey Committee, Saburo Koji / Omi Letter III) 185 pages, 7. Figure 5 (b)) Mitsui east pressure type reaction tank of the same type, and it is shown divided into 10 segments C 1 / C 0 = 〇. 9 5 5 things) and two 10-liter complete mixing tanks in a continuous continuous line -29-200415093 Polymerization device to produce thermoplastic resin. The plunger flow tower type reaction tank system constitutes a particle formation process, the first complete mixing tank of the second reaction tank system constitutes a particle diameter adjustment process, and the third reaction tank system constitutes a post-polymerization process. In the aforementioned plunger flow tower type reaction tank, 22 parts by weight of acrylonitrile, 25 parts by weight of ethylbenzene, and 13 parts by weight of styrene-butadiene rubber (made by Japan * # ^ 'Co., Ltd.) S310S), 0. 2 parts by weight of t-lauryl mercaptan, 005 parts by weight of butylperoxy) 3,3,5-trimethylcyclohexane, a raw material composed of 3,3,5-trimethylcyclohexane, which is continuously supplied to a three-stage stirred polymerization tank reaction at 10 kg / hour Device to polymerize the monomers. The first plunger-flow tower type reaction tank was set to 8 8 t, and the second reaction tank was set to 1 2 5. (:, And the third reaction tank is set to 140 ° C. The polymerization solution from the third reaction tank is supplied to the removal formed by the preheater (21 0 ~ 250 ° C) and the decompression chamber (40 To rr) After the volatile device, a thermoplastic resin (5) in which rubber particles are dispersed is obtained via an extruder. The weight average particle diameter of the obtained rubber dispersed phase is 0. 5 microns. [Examples 1 to 5, Comparative Examples 1 to 4] The resin obtained in Synthesis Examples 1 to 5 and the following antistatic agent were mixed in accordance with the mixing ratio shown in Table 彳. Use 40 with an outlet. Millimeter biaxial extrusion ("TEX-44" manufactured by Japan Steel Works Co., Ltd.) was melt-kneaded at 200 ° C and cut to obtain nine pellets. That is to say, the present nine-grain system was subjected to a volatile removal treatment once. The antistatic agent used here -30- 200415093 is "Breststatt NC6321" (polyetheresteramide, manufactured by Sanyo Chemical Industry Co., Ltd., with a refractive index of 1. 516) and sodium lauryl benzosulfonate. The melt flow rate, ash content, and 4-vinylcyclohexene content of the obtained nine pellets were measured according to the following methods. The measurement results are shown in Table 1. Using the obtained nine pellets, using an injection molding machine of J450E-C5 manufactured by Japan Steel Manufacturing Co., Ltd., at a resin temperature of 200 ° C, a mold temperature of 50 ° C, an injection speed of 45 mm / sec, and an injection pressure of 1 600 kg / cm 2 is injection-molded to form a container as shown in FIG. 1. Examples 1 to 5 and Comparative Examples 1 to 4 respectively gave molded articles having good appearance. However, in Examples 4 and 5, the interior was difficult to see because it was cloudy. The sensory evaluation of odor was performed in accordance with the following method. The evaluation results are shown in Table 2. (1) Melt flow rate Based on ASTM D-1 238, the melt flow rate (g / 10 minutes) was measured. The measurement temperature was 220 ° C, and the load was 10 kg. (2) The ash is measured in a platinum crucible. Nine samples with a measured dry weight of about 10 grams are accurately measured. After being turned on an electric cone furnace installed in a ventilated chamber, the temperature is set to 80 ° C. The platinum crucible in the electric furnace was removed and left for 4 hours. Then the platinum crucible was taken out and dried in a desiccant. The weight was measured and the ash content (%) was calculated from the weight difference. (3) 4-vinylcyclohexene Content-3 1-200415093 Nine grains of the sample were dissolved in dimethylformamide, and a 5 8 9 0 Π type gas chromatography analyzer manufactured by Harvey Parker Co., Ltd. with a flame ion detector (FID) was used for analysis. 4-vinylcyclohexene content in the sample solution. For the quantification, a calibration curve was prepared using a solution of 4-methylcyclohexene at a known concentration in dimethylformamide. (4) Total light transmittance A test piece of 3 mm was used, and it was measured using a reflection and refractive index instrument H R -1 0 0 manufactured by Murakami Color Technology Co., Ltd. (5) Fog Using the same test piece as for measuring the total light transmittance, the measurement was performed using a reflection and refractive index instrument H R -1 0 0 manufactured by Murakami Color Research Laboratory Co., Ltd. (6) Based on AST M D-2 56, measure the Izod impact strength (Mpa) attached to the notch. (7) Use a 3 mm test piece for static electricity prevention, adjust the state for 1 month at 23 ° C, 50% R Η humidity, and measure the water washing with a super ohm meter SN8210 made by Toa Electronics Industry Co., Ltd. Surface inherent resistance 前后 (Ω) before and after treatment. (8) Odor sensory evaluation The container obtained by injection molding was placed in an open space at room temperature for 24 hours, and the upper box and the lower box were fitted and sealed at room temperature for 1 hour. Then, five odor-sensitive testers sniffed the degree of odor after opening the box -32- 200415093 to evaluate the odor function. The evaluation was performed based on the following criteria. 5 points: The odor is obvious and strong; 4 points: The odor is considered to be quite; 3 points: The odor is felt; 2: The odor is slightly smelled; 1: The odor is not felt.
-33- 200415093 -3t 表面固有電阻値(水洗後：Ω) 表面固有電阻値(水洗後：Ω) 耐衝擊性(Mpa) 霧傾％) 全光線穿透率(％) 4-乙烯基環己烯含量(ppm) 灰分(％) MFR(克/10分鐘） <評價結果> 月桂醯基苯并磺酸鈉 聚醚酯醯胺 橡膠粒子分散樹脂(5) 苯乙烯系聚合物(4) 苯乙儲系聚合物(3) 接枝共聚合樹脂粒子(2) 接枝共聚合樹脂粒子(1) <摻混比(重量份)> GO X _ Ο CO GO X _x Ο CO —λ ro 00 ⑦ αι ο ο _X Ν3 ro cn αι 〇 〇〇 〇 —X 實施例 σ> X ο ο σ> X ο -A cn _x 00 ho cn CD Ο on ο Ο ΓΟ Κ) o ^1 〇 0J 〇 Κ) X _X ο ϋΐ 払 X ο ro cn 扛 αι 00 σ> cn ο ο —Λ ro K) K) -ν| 〇 〇〇 〇 to X —X ο α -nJ X 〇 Oi 00 o 00 cn ΟΊ ο ο ο ο _V ro 1 00 払 4^ X _χ Ο 03 cn X _V o CO CO Ol Ο cn ο ο Ο Ο _Λ. —X αι 1 00 cn 4^ X Ο σ> X _^ o cn σ> 00 00 00 300 Ο Κ) cn ro ND -vl 〇 00 〇 比較例 Κ) X __χ Ο CO ho X — o CO _X o αι 00 CO 300 ο κ> ΟΊ K3 00 cn 〇 C0 〇 ro cn X ο ro cn X o ro K> cn ro 00 KD ο 0.001 00 o 00 1 00 OJ 00 X _Α ο cn> 00 X -A o cn —Λ. CD 〇 0.001 N3 —λ 1 00 • u 200415093 丨35丨 評價平均 測試人員V 測試人員IV 測試人員m Sm > 1=1 測試人員I ho -m Πτ OJ g? ro g? ro m ho g? OJ D? 實施例 ho σ> Π-γ CO m 00 g? ho §? ro g? GO 罌 ro Κ) ⑦ GO S? M (X> ho s? CO -m Π-γ GO h〇 S? tU43 灃 K> g? 払 g? —λ. m Ώ-r m Ehr ND m Ώ-r K) m Ώ-τ _λ tUEI D? ΟΊ ting D? cn B? m Ό-Γ cn m Ώ-τ vm Ώ-τ 仁 m n-r 比較例 5.0點 Ol m Dt (S\ m Ώ-τ cn m Πτ cn -m Πτ on g? K) _Λ m Π-γ _x -m Ώ-r -A (v〇 m Ώ-τ ro g? —λ. vm Π-γ GO ro J-TP _ m Ώ-r —1 —X m Dt _x 網 Ehr ro 200415093 由以上之結果可明白，於製造接枝共聚合共聚合 樹脂粒子時，除了使用酸予以凝固並且強化洗淨作業， 將以此作法所得到的樹脂粒子、與溶液聚合之苯乙烯 系聚合物一起混合而製造熱可塑性樹脂之實施例 1〜3，係顯示出低的灰分。又，不具有乳化聚合製程 而合成分散有橡膠粒子之熱可塑性樹脂的實施例4及 5也顯示出低的灰分。相對的，具有使用金屬鹽予以 鹽析，並僅實施一般之洗淨作業之乳化聚合製程之比 較例1及2，則灰分量就變高。 又且，於製造接枝共聚合共聚合樹脂粒子時實施 水蒸氣蒸餾作業，將如此作法所得到的樹脂粒子，與 溶液聚合之苯乙烯系聚合物一起混合而製造熱可塑性 樹脂之實施例1〜3，其4-乙烯基環己烯含量降低，且 臭氣官能分散有橡膠粒子之熱可塑性樹脂的實施例4 及5，其4-乙烯基環己烯含量也降低，且臭氣官能評 價之結果也是良好的。 再者，使用聚醚酯醯胺做爲靜電防止劑之實施例 1及5，可得到洗淨前後均爲良好之靜電防止效果，然 而不使用靜電防止劑之實施例2及4，洗淨前後之表 面固有電阻値變高，以致靜電防止性不足夠。就使用 月桂醯基苯并磺酸鈉做爲靜電防止劑之實施例3而 言，雖然洗淨前後之表面固有電阻値降低，但是洗淨 後之表面固有電阻値卻變高，就靜電防止效果之持續 -36- 200415093 後之表面固有電阻値卻變高，就靜電防止效果之持續 性特點來看是不夠充分的。又，不含二烯系橡膠粒子 之比較例3及4，耐衝擊性變差。 【實施例6〜9】（成形溫度之影響） 使用和在實施例1中所使用的同樣之熱可塑性樹 脂九粒，利用日本製鋼所股份有限公司製 J 4 5 0 E - C 5 之射出成形機，如表3所示變他滾筒設定溫度，以模 具溫度爲50 °C、射出速度爲45毫米/秒、射出壓力爲 1 600公斤/平方公分進行射出成形，製做成如第1圖 所示之容器。就此等容器，依照下述之方法進行成形 成性及有機物量之評價。將結果示於表3。 (9)成形性 觀察樹脂之充塡性，當樹脂可以完全充塡於容器 形狀的情形記爲〇，當樹脂不能完全充塡於容器形狀 的情形記爲X。 (1 〇)分解有機物量 從成形後之製品採取1 〇毫克之試樣，於1 50 °C下 保持1 〇分鐘後，測定於1 0分鐘內所產生的有機氣體 量，測定裝置係使用哈維特帕克得公司製G-1 8 00 A型 氣體色譜分析儀。計算出有機氣體量之換算成苯乙烯 之値。 -37- 200415093 丨38丨 SI .通風脫除揮發分次數 (次） 有機氣體量（ppm) 成形性 ii Et bl·園 V__^ 射出速度（毫米/秒） 模具溫度（°C) 滾筒設定溫度（°C) 700 〇 1600 4^ cn cn ο 240 _X G) 500 〇 1600 〇1 αι ο 220 實施例7 400 〇 1600 cn cn ο 200 ϊι| 諸 00 350 X 1600 ΟΊ cn ο 1 80 ϋ| 諸 CD 300 〇 1600 仁 ΟΊ cn ο 200 h〇 實施例1 〇 1 50 〇 1600 仁 ΟΊ CJI 〇 200 實施例1 1 200415093 由以上之結果可明白：隨著成形溫度之降低，脫 除氣體之總量會減少。此種事實顯示出：射出成形時 之有機化合物的分解量會隨著射出溫度之上昇而增 加。就提供本次成形之熱可塑性樹脂而言，當射出成 形之際的熔融樹脂溫度爲1 8 0 °C時雖然成形性會下 降，然而在200 °C就可以得到良好的成形品。又且可 明白：藉由反復地進行在化合物後之脫除揮發分作業， 可以大幅地減少成形品中之有機揮發成分之量。 【產業上利用可能性】 t 本發明之淸淨室用容器在成形時的尺寸精度、成 形品表面之平滑性、剛性、耐衝擊性等之平衡上均優 異，且樹脂成本比較低，以及灰分也最少致使成爲因 金屬離子而起的污染源之可能性變低的緣故，所以具 有可做爲被使用於淸淨室內之容器的優異性能。從而， 特別地有用於做爲半導體基板、顯示裝置基板、及記 錄媒體基板等之容器。 【圖式簡單說明】 第1圖爲顯示在本發明之實施例中成形的容器之 全體構造之分解斜視圖。圖中分別表示：彳爲容器、2 爲上盒子、3爲下盒子。 【元件符號對照表】 1 容器 2 上盒子 3 下盒子 -39--33- 200415093 -3t Surface specific resistance 値 (after washing: Ω) Surface specific resistance 値 (after washing: Ω) Impact resistance (Mpa) Mist tilt%) Full light transmittance (%) 4-vinylcyclohexane Olefin content (ppm) ash content (%) MFR (g / 10 min) < Evaluation result > sodium lauryl benzosulfonate polyetherester fluorene rubber particle dispersion resin (5) styrenic polymer (4) Styrene storage polymer (3) Graft copolymerized resin particles (2) Graft copolymerized resin particles (1) < Mixing ratio (parts by weight) > GO X _ Ο CO GO X _x Ο CO —λ ro 00 ⑦ αι ο ο _X Ν3 ro cn αι 〇〇〇〇—X Example σ > X ο ο σ > X ο -A cn_x 00 ho cn CD 〇 on ο Ο ΓΟ Κ) o ^ 1 〇0J 〇Κ ) X _X ο ϋΐ 払 X ο ro cn Carry αι 00 σ > cn ο ο —Λ ro K) K) -ν | 〇〇〇〇to X —X ο α-nJ X 〇Oi 00 o 00 cn ΟΊ ο ο ο ο _V ro 1 00 払 4 ^ X _χ Ο 03 cn X _V o CO CO Ol Ο cn ο ο Ο Ο Ο _Λ. —X αι 1 00 cn 4 ^ X Ο σ > X _ ^ o cn σ > 00 00 00 300 Ο Κ) cn ro ND -vl 〇00 〇 Comparative example Κ) X __χ 〇 CO ho X — o CO _X o α 00 00 300 ο κ > ΟΊ K3 00 cn 〇C0 〇ro cn X ο ro cn X o ro K > cn ro 00 KD ο 0.001 00 o 00 1 00 OJ 00 X _Α ο cn > 00 X -A o cn — Λ. CD 〇0.001 N3 — λ 1 00 • u 200415093 丨 35 丨 Evaluate average tester V Tester IV Tester m Sm > 1 = 1 Tester I ho -m Πτ OJ g? ro g? ro m ho g? OJ D? Example ho σ > Π-γ CO m 00 g? ho §? ro g? GO opiaro Κ) ⑦ GO S? M (X > ho s? CO -m Π-γ GO h〇S? tU43 沣 K > g? 払 g? —λ. m Ώ-rm Ehr ND m Ώ-r K) m Ώ-τ _λ tUEI D? ΟΊ ting D? cn B? M Ό-Γ cn m Ώ-τ vm Ώ-τ Ren m nr Comparative example 5.0 points Ol m Dt (S \ m Ώ-τ cn m Πτ cn -m Πτ on g? K) _Λ m Π-γ _x -m Ώ-r -A (v〇m Ώ-τ ro g? —λ. vm Π-γ GO ro J-TP _ m Ώ-r —1 —X m Dt _x net Ehr ro 200415093 It is understood that in the production of the graft copolymerized copolymerized resin particles, in addition to coagulation with an acid and intensive cleaning operations, the tree obtained in this way will be used. Particles, mixed together with the polymerization of the styrenic polymer solution produced thermoplastic resin of Example 1 ~ 3, lines showed a low ash content. In addition, Examples 4 and 5 in which a thermoplastic resin having dispersed rubber particles was synthesized without an emulsion polymerization process also showed a low ash content. In contrast, when the ratio of the emulsification polymerization process in which salting out is performed using a metal salt and only ordinary washing operations are performed is compared with Examples 1 and 2, the ash content becomes higher. In addition, in the production of graft copolymerized copolymer resin particles, steam distillation was performed, and the resin particles obtained in this way were mixed with a solution-polymerized styrene polymer to produce a thermoplastic resin. Examples 1 to 1 3. In Examples 4 and 5 in which the 4-vinylcyclohexene content was reduced and the odor-functional thermoplastic resin was dispersed in rubber particles, the 4-vinylcyclohexene content was also reduced and the odor function was evaluated. The results are also good. Furthermore, Examples 1 and 5 using polyetheresteramide as an antistatic agent can obtain a good antistatic effect before and after washing, but Examples 2 and 4 without using an antistatic agent before and after washing The surface intrinsic resistance 表面 becomes so high that the static electricity prevention property is insufficient. In Example 3 using sodium lauryl benzosulfonate as an antistatic agent, although the inherent resistance 値 on the surface before and after washing was reduced, the inherent resistance 値 on the surface after washing was increased, and the antistatic effect was achieved After the continuous -36- 200415093, the inherent resistance of the surface becomes high, which is not sufficient in terms of the continuous characteristics of the antistatic effect. In addition, Comparative Examples 3 and 4 containing no diene rubber particles had poor impact resistance. [Examples 6 to 9] (Effect of molding temperature) Nine pellets of the same thermoplastic resin as those used in Example 1 were used for injection molding by J 4 50 0 E-C 5 manufactured by Japan Steel Works Co., Ltd. The machine, as shown in Table 3, sets the temperature of the other rollers. The mold temperature is 50 ° C, the injection speed is 45 mm / sec, and the injection pressure is 1 600 kg / cm2. Shown container. For these containers, the moldability and the amount of organic matter were evaluated in accordance with the methods described below. The results are shown in Table 3. (9) Formability Observe the filling property of the resin. When the resin can completely fill the shape of the container, it is recorded as 0, and when the resin cannot be completely filled with the container shape, it is recorded as X. (10) Amount of decomposed organic matter: A sample of 10 mg is taken from the molded product, and it is held at 150 ° C for 10 minutes, and then the amount of organic gas generated within 10 minutes is measured. G-1 8 00 A gas chromatograph made by Witt Parker. Calculate the amount of organic gas and convert it to styrene. -37- 200415093 丨 38 丨 SI. Number of volatiles deaeration (times) Organic gas amount (ppm) Formability ii Et bl · Park V __ ^ Injection speed (mm / s) Mold temperature (° C) Roller setting temperature ( ° C) 700 〇1600 4 ^ cn cn ο 240 _X G) 500 〇1600 〇1 αι ο 220 Example 7 400 〇1600 cn cn ο 200 | ι | 00 00 350 X 1600 ΟΊ cn ο 1 80 ϋ | CD 300 〇1600 Ί〇Ί cn ο 200 h 〇 Example 1 〇1 50 〇1600 Ί〇Ί CJI 〇200 Example 1 1 200415093 It can be understood from the above results that as the molding temperature decreases, the total amount of gas removed will decrease. This fact shows that the amount of decomposition of the organic compound during injection molding increases as the injection temperature increases. In terms of providing the thermoplastic resin for this molding, when the temperature of the molten resin at the time of injection molding is 180 ° C, although the moldability decreases, a good molded product can be obtained at 200 ° C. It is also clear that the amount of organic volatile components in the molded product can be greatly reduced by repeatedly performing the operation of removing volatiles after the compound. [Industrial Applicability] t The clean room container of the present invention is excellent in the balance of dimensional accuracy during molding, smoothness, rigidity, and impact resistance of the surface of the molded product, and has a relatively low resin cost and ash It also minimizes the possibility of becoming a source of pollution due to metal ions, so it has excellent performance as a container that can be used in clean rooms. Therefore, it is particularly useful as a container for semiconductor substrates, display device substrates, and recording medium substrates. [Brief Description of the Drawings] Fig. 1 is an exploded perspective view showing the overall structure of a container formed in an embodiment of the present invention. The figures show: 彳 is a container, 2 is an upper box, and 3 is a lower box. [Comparison of component symbols] 1 container 2 upper box 3 lower box -39-