1293934 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。聚羧酸酯雖然透明且耐衝擊性均優，但是要能保 持原來之透明性地進行靜電防止處理卻有困難，因而 樹脂成本高。又，丙烯腈-苯乙烯共聚物（ABS樹脂）及 甲基丙烯酸甲酯-苯乙烯（M S樹脂）雖然是透明的，然 1293934 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 酞酸丁二醇酯（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ABS)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9-92714號公報上設載著一種成 定形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230至24 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 1293934 使用於1C載體容器。 又，特開平9-59462號公報上記載著一種殘留苯 乙烯系單體及殘留4-乙烯環己烯中任何一種均在一定 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ABS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ABS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A B S樹脂上之代表性方法，係爲一種 1293934 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ABS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ABS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ABS樹脂，然而做成家電製品之外殼 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，分散有以二燃 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。 1293934 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 ABS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、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- 1293934 較理想。 又，前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100 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150°C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 2 0%以下之樹脂。又且，理想上，爲一種將射出成形時之 滾筒設定溫度設在220 °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， -11- 1293934 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 是苯乙烯、α -甲基苯乙烯、對甲基苯乙烯等，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 表的不飽和殘酸烷酯單體，丙嫌酸、甲基丙燃酸、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、〇-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， -12- 1293934 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。藉由與胺化乙稀單體共聚合，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 50重量％以上，更宜是在80重量。/。以上。被使用來做 爲二烯單體，舉例來說，例如其可以是彳，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 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 〇 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5〜50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 1293934 之物。此種組成比例’係爲表不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 族二儲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 〇重量％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10〜90重 量％。當小於1 〇重量％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2〇重量％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 - 1293934 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， 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嫌單體 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。 1293934 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- 1293934 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。 其他理想的製造方法之一，係爲一種將由二燃單體 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- 1293934 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0.18重量％ 以下，更宜是在0.15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1〇〇 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 -18- 1293934 己烯含量較宜是在80 ppm以下，更理想是在6〇 ppm以 下。 在具有乳化聚合之情況下，爲了降低彳，3 _ 丁二嫌之 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心乙烯環 己烯。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3 0分鐘以上之時間來進行水蒸氣蒸餾 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-乙烯環己烯之含有量。具 體而言，於聚合物終了之後，較宜是以1 8 0。(：以上、 更理想爲200°C以上之溫度，減壓到1〇〇 Torr以下、 理想上在50 To「「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 -1 9 - 1293934 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- 1293934 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 .4 8〜 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。循對於此，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- 1293934 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。 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160〜220°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 °C、1 0公斤荷重）雖然並沒有特別地限定，然而通常是 1〜1 〇〇克/1 0分鐘。依照成形性的觀點來看，較宜是5 -22 - 1293934 克/1 0分鐘以上，依照強度的觀點來看，較宜是在5 Ο 克/1 〇分鐘以下。 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20%以下之樹脂。藉著使具有20% 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80%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22 CTC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220 -23- 1293934 °c以下，可望將樹脂之分解抑制到最低限度。 成形之樹脂之熔融時間通常不是愈長愈好，於 途上，考慮成形性及成形速度較宜是以足夠高 形；就供於淸淨室內使用目的而言，不僅可以 熔融時之熱分解所發生的有機物量則是重要的。 較宜是將可能成形溫度下降到最低成形溫度。 形溫度係因樹脂之組成及熔融流速而不同，考 因素而加以設定。例如，增加樹脂中的不飽和 酯單體由來成分之比例，可容易使得以比較低 形。射出成形時之滾筒設定溫度較理想的是在 以下，更理想的是在 20CTC以下。又且，通 1 6 0 °c以上。 另外，射出成形時之熔融樹脂溫度，也會 在樹脂中的添加劑之熱分解行爲產生影響。例 用於本發明之淸淨室用容器的熱可塑性樹脂中 是含有靜電防止劑，其中較理想的是聚醚酯醯 經在前面說明了。熔融成形時，雖然是微量， 靜電防止劑也會熱分解。此時，就以高溫成形 因熱分解而發生的低分子量之胺及醯胺（包括 量會增加。胺及醯胺會溶出於水中透過處理液 污染半導體晶圓，更且由於含有此種氣兀素之化 在熱擴散處理等之半導體製造程序中，有可能 及胺等之鹼性物質的緣故，因而是比一般的僅 在射出 普通用 溫來成 減低因 從而， 可能成 慮此等 羧酸烷 溫來成 2 1 0°C 常是在 對摻混 如，使 ，較宜 胺，已 但此種 而言， 勺酯）的 而容易 合物， 產生氨 由碳、 -24- 1293934 氫、氧所構成的有機化合物比起來更令人嫌惡的 源。從而，尤其是在使用含有像這樣的氮元素之 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 有的分解有機物之量，較宜是儘可能地少。具體而 將從成形品切削出的試料於1 50°C下保持1 0分 後，於10分鐘內所產生的有機氣體量之苯乙烯換 較宜是在600 ppm 以下。比較理想的是在400 以下，更理想的是在3 0 0 p p m以下。將分解有機 量減低到像這樣時，在製造如前述這樣的樹脂時 有效地減低揮發成分，並且同時有效地儘可能的 來成形。 本發明之淸淨室用容器是一種可在淸淨室內 的容器’是一種收容原料、中間製品或製品用之容 並沒有特別地限定。舉例來說，例如是收納半導 板、顯示裝置基板及記錄媒體基板中所選出的板 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 ^板 '太陽電池製造用之基板等。此種材料並沒 別地限定於以矽爲代表之物。又，其形態可以是 晶圓這樣的圓形，也可以是像太陽能電池這樣的 形°又’將矽晶圓圓切斷成晶片的形態也沒有關 其中之代表性的實施態樣，係矽晶圓用容器 污染 靜電 所含 言， 鐘之 算値 ppm 物之 就可 低溫 使用 器， 體基 狀體 用的 有特 像矽 四方 。近 -25- 1293934 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 顯不裝置製造用基板等。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- 1293934 此種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 % )、〇 · 1份之乙；(¾二胺四乙酸納、〇 · 〇 部硫酸鐵、 〇·3份之甲醛磺酸鈉，加熱至60 °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- 1293934 的混合物，更且進一步於60 °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 00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I留。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，與合成例彳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130份之純水 及〇 . 3份之高硫酸鉀後，在攪拌下昇溫至6 5 t。之後， 再以4小時分別地連續添加由1 〇份之丙烯腈、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- 1293934 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100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3 0份之苯乙烯、7 0份之甲基丙烯酸甲酯、 10重量份乙基苯、〇·〇5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 5〇t，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10段C1/C0 = 0.955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- 1293934 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22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（日本份有限公司製S3 10S)、0.2重量 份之卜月桂基硫醇、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88°C、第2反應槽設定爲125°C、 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（2 1 0〜2 5 0 °C )和減壓室（4 0 T 〇 r r)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 止劑依照表彳所示之摻混比例混合，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 200 °C熔融混 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- 1293934 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，折射率爲彳.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 -乙燦基環己嫌含量。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 6 0 0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AST M D-1 238爲基準，測定熔融流速（克/10分 鐘）。測定溫度爲2 2 (TC，荷重爲1 0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 10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80(TC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- 1293934 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 Ο 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 00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 HR-100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卜 (7) 靜電防止性 使用爲3毫米之試驗片，於23°C、50%RH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24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- 1293934 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。 1293934 — 34丨 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) 霧値(％) 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) 苯乙烯系聚合物(3) 接枝共聚合樹脂粒子(2) 接枝共聚合樹脂粒子(υ <摻混比(重量份)> 00 X 〇 CO X _A Ο 03 ho 00 σ> cn ο ο Κ) h〇 cn cn 〇 0J 〇 實施例 X 〇 σ> X ο 02 00 ND cn CO ο cn ο ο -Λ. hJ h〇 o 〇 CO 〇 ho X 〇 cn X -Λ. Ο ΓΟ ΟΙ οι 00 σ> cn ο ο -1. Κ) KD ho VI 〇 00 〇 CO X -λ 〇 05 -νΐ X -λ. Ο 05 CJ ο CO cn cn ο ο ο ο -JL ro 1 00 X -X 〇 C0 ΟΙ X -Λ. ο 00 C0 αι 扛 ο cn ο ο ο ο -Α _^ cn 1 00 cn X 〇 σ> 4^ X __Λ. Ο 05 0J 00 00 300 ο κ> ΟΊ M ro -vl 〇 C0 ο 比較例 ro X -χ ο CO Κ) X ο CO ο αι 00 CO 300 ο ro ΟΊ M 00 cn 〇 CO ο Ν) ΟΊ X _Χ Ο ΙΟ σι X _χ Ο ΓΟ ΓΟ U1 ho 00 ro ο 0.001 CO o 00 100 LO 00 X -X Ο CT) 00 X _X Ο σ> _X CD ο 0.001 K) 1 00 1293934 -35丨 評價平均 測試人員v 測試人員IV 測試人員Π 測試人員π 測試人員I ND 仁 tUEJ 05 g? Μ S? ro 灃 ho §? 〇〇 turn S? 實施例 K) ⑦ g? CO m CO \\m Π-γ κ> B? ro B? OJ iUS 鎞 ro N> Ο) m n-r CO ho CO ho russ n? CO g? 03 to m «Jk tUJZI D? -Jk g? M n? g? tUS D? ro ho g? g? cn 4.4點 cn §? m rhr σι S? vm O-r 比較例 σι ο g? cn g? σι tuss D? cn g? cn m Ut Ol μ _1 g? _^ g? —X m Ώ-r h〇 m n-r hO vm D-p _1 §? CO —X N) g? _x 測 Π-Γ _X m rhr Λ_Χ m U-r _x m Ehr ho 觀 Dt 1293934 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- 1293934 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J450E-C5 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10毫克之試樣，於150 °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 0 0 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 - 1293934 丨38丨 =1 .通風脫除揮發分次數 (次） 有機氣體量（ppm) 成形性 bf Μ 射出速度（毫米/秒） 模具溫度（°C) 滾筒設定溫度（°C) 700 〇 1600 4^ 〇1 cn ο 240 )Β| 譜 G) 500 〇 1600 cn cn ο 220 —λ 實施例7 400 〇 1600 仁 cn cn ο 200 Μ 00 350 X 1600 仁 cn cn ο 1 80 諸 CD 300 〇 1600 仁 cn αι ο 200 Μ 實施例1 〇 1 50 〇 1600 〇1 cn ο 200 實施例11 1293934 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 80 °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】 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】 弟1圖爲顯不在本發明之貫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：1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1293934 玖, DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a container for a clean room. More specifically, the present invention relates to a masterbatch resin composed of an aromatic vinyl monomer and another monomer copolymerizable, which is obtained by dispersing a diene monomer as a main component. a thermoplastic resin composed of olefinic rubber particles, the ash of the thermoplastic resin is 0. 2% by weight or less of the clean room container. [Prior Art] In order to prevent contamination of a wafer in a semiconductor manufacturing process, a glass substrate in a liquid crystal panel manufacturing process, or a metal disk in a hard disk manufacturing process, it is treated by a clean room. In these manufacturing procedures, various containers are used in order to enable efficient disposal of such substrates. For example, there is a case where a plurality of substrates are accommodated at the same time, and the container used in the case of transporting the specific process from the cleaning chamber to the container used in the next process is also housed in the container and various treatments are performed in situ. Resins used as container materials are available in a variety of ways depending on their purpose. For example, although polypropylene is inexpensive, it cannot be used for applications requiring transparency, dimensional accuracy during molding, rigidity, and the like. Although the polycarboxylate is transparent and excellent in impact resistance, it is difficult to carry out static electricity prevention treatment while maintaining the original transparency, and thus the resin cost is high. Further, although the acrylonitrile-styrene copolymer (ABS resin) and the methyl methacrylate-styrene (MS resin) are transparent, 1293934, in addition to poor impact resistance, the crucible is easily worn by sliding rubbing, in particular It is difficult to use in a clean room that is abandoning pollution. Further, poly(p-butylene phthalate) (PBT) and polyetheretherketone (PEEK) are excellent in heat resistance, but are opaque and have high resin cost. Acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) and resins similar thereto are excellent in balance of dimensional accuracy during molding, smoothness of surface of molded article, rigidity, impact resistance, and the like, and A general-purpose resin with a relatively low resin cost. As described below, permanent static electricity prevention and handling properties can also be provided. For example, Japanese Laid-Open Patent Publication No. Hei 9-92714 discloses a semiconductor wafer storage static electricity prevention container having a predetermined shape. In the examples of the publication, there is described an example (Examples 1, 3 and 4) in which a container formed by injection molding at 230 to 240 ° C using an ABS-based permanent static electricity prevention resin. The container described in the examples had excellent static electricity prevention properties and was excellent in transparency depending on the product (Example 3). JP-A-62-1 1 9256 discloses a copolymer mixture composed of a (meth) acrylate monomer and another copolymerizable vinyl monomer in the presence of a rubbery polymer. In the polymer obtained by polymerizing a branch, a thermoplastic resin composition formed by blending a polyether ester decylamine. It is also described that such a resin composition is excellent in permanent static electricity prevention, impact resistance, and transparency, and can be used for preventing the occurrence of a barrier due to static electricity. For example, it can be used in a 1C carrier container at 1293934. Further, Japanese Laid-Open Patent Publication No. Hei 9-59462 discloses that any one of a residual styrene monomer and residual 4-ethylenecyclohexene is less than a certain amount, and the average particle diameter of the rubber particles and their distribution are within a certain range. ABS resin composition. When such a resin composition is used, it is possible to produce an odorless product which is excellent in impact strength and tensile strength and which has good gloss. It is also described in the publication that ABS resin can be used for an outer casing of a home electric appliance and a molded article of a vehicle. An electrostatic discharge container for semiconductor wafer storage formed of an ABS resin is known as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. However, as a resin used in a clean room container, ABS and the like are practically practically unusable. One of the reasons for most of this is because of the problem of the source of pollution described below. In the case of containers used in a clean room, most of the items to be stored are extremely repellent, so it is very important that the containers cannot become a source of pollution. Of particular concern in contaminants is contamination due to metal ions. For example, in the semiconductor manufacturing process, there is a concern that in the diffusion operation, the impurities of the metal ions may diffuse into the circuit to increase the defect rate. Further, it is necessary to simultaneously prevent contamination by organic substances other than metal ions. However, a representative method for producing A B S resin is a process in which 1293934 includes a diene rubber particle obtained by emulsion polymerization, which is graft-modified in an emulsion. In order for the polymerization in the emulsion to proceed smoothly, it is necessary to have a large amount of emulsifier, which in most cases is a surfactant composed of a metal salt. Further, the obtained grafted rubber particles are solidified and need to be separated from the emulsion. However, in most cases, salting out is carried out, and in this case, the coagulum further contains a large amount of salt. As a result, most of the ABS resin sold in the market has a considerable amount of metal salt component remaining. Therefore, it is far from being a substance having a possibility of becoming a source of pollution, so that ABS and its similar resin are hardly used today as a material for a clean room container. Japanese Patent Publication No. Hei 9-59462 discloses an ABS resin having a small amount of residual organic matter. However, the outer casing and the vehicle molded article of the household electrical appliance have a problem of odor, not to mention a source of pollution in the clean room. problem. The present invention is to solve the above problems, and to provide a container for a clean room which is composed of ABS and a similar thermoplastic resin, and which has a low ash content and is less likely to be contaminated by metal ions. purpose. A container for a clean room is obtained by dispersing a diene system obtained by polymerizing a secondary combustion monomer as a main component resin composed of an aromatic vinyl monomer and another monomer copolymerizable. It is formed of a thermoplastic resin composed of rubber particles, and the ash of the thermoplastic resin is 〇 2 by weight. /. the following. 1293934 A container which is very suitable for accommodating a plate-shaped body selected from a semiconductor substrate, a display device substrate, and a recording medium substrate. By this, a container for a clean room formed of ABS and the like, but having at least a ash content which is difficult to be a metal contamination source is provided. SUMMARY OF THE INVENTION The above problems are achieved by providing a dispersion of a diene monomer as a main component in a masterbatch resin composed of an aromatic vinyl monomer and another monomer copolymerizable. A thermoplastic resin composed of the formed diene rubber particles is formed, and the ash content of the thermoplastic resin is achieved in a clean room container of 2% by weight or less. In this case, the other monomer copolymerizable as described above is desirably at least one selected from the group consisting of a vinyl cyanide monomer and an unsaturated alkyl carboxylate monomer. Further, the thermoplastic resin is desirably 5 to 50% by weight of a diene rubber, 10 to 90% by weight of an aromatic diene monomer, and 10 to 90% by weight of the other copolymerizable other single The body is polymerized. In the embodiment of the thermoplastic resin, an aromatic vinyl monomer and other copolymerizable monomers are dispersed in an emulsion in which diene rubber particles obtained by polymerizing a diene to a diene monomer are dispersed. A graft resin obtained by copolymerizing a monomer and a resin obtained by copolymerizing a copolymer of an alternative aromatic vinyl monomer and another monomer copolymerizable are melt-mixed. Further, in this case, it is preferred to use a small amount of acid to coagulate the graft copolymer resin particles, wash them, and then supply them to a melt mixing ratio of -10- 1293934. Further, the thermoplastic resin is a type in which a diene rubber obtained by polymerizing a diene monomer is dissolved in an aromatic vinyl monomer and another monomer copolymerizable, and then the aforementioned aromatic vinyl monomer is obtained. , It is also an ideal embodiment to polymerize with other monomers which can be copolymerized. The above diene monomer is desirably 1,3-butadiene, and the thermoplastic resin has a vinylcyclohexene content of 100 ppm or less. The thermoplastic resin desirably contains an antistatic agent formed of a polyether ester decylamine or an antistatic agent composed of conductive carbon. Preferably, the sample cut from the molded article is held at 150 ° C for 10 minutes, and the amount of organic gas generated in 10 minutes is converted to styrene of 600 ppm or less. Preferably, the thermoplastic resin is a resin having a haze of 20% or less when the molded article having a thickness of 3 mm is formed. Further, it is preferable that the drum set temperature at the time of injection molding is set to 220 ° C or lower and then injection molded. In a preferred embodiment of the present invention, the above-described clean room container for accommodating 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 a clean room of the present invention is a masterbatch resin composed of an aromatic vinyl monomer and another monomer copolymerizable, and -11-1293934 is dispersed and polymerized by a diene monomer. A product formed of a thermoplastic resin composed of diene rubber particles. The thermoplastic resin used in the present invention is an aromatic vinyl monomer. A product formed from a copolymer between other monomers copolymerizable. It is not a polymer composed only of an aromatic vinyl monomer, and by forming a copolymer with other monomers, it can be easily made into excellent impact resistance, transparency, heat resistance, chemical resistance, and the like. Resin. These polymers are usually a random copolymer. The aromatic vinyl monomer to be used herein may, for example, be styrene, α-methylstyrene or p-methylstyrene, and one or more of these may be used. The other monomer which can be copolymerized is not particularly limited as long as it can be copolymerized with the aromatic vinyl monomer. For example, it may be acrylonitrile, methacrylonitrile or the like. Aminated ethylene monomer represented by acrylate, unsaturated with typified by (meth) acrylate such as methacrylate, ethyl acrylate, methyl methacrylate or ethyl methacrylate Residual acid alkyl ester monomer, unsaturated carboxylic acid or unsaturated dicarboxylic anhydride monomer such as acrylic acid, methyl propylene acid, maleic acid, maleic anhydride, citraconic anhydride, maleimide, methyl A maleic acid-based monomer such as maleic amine, ethyl maleamide, stilbene-phenylmaleamide or guanidine-chloro-indole-quineic acid guanamine. ‘One or two or more of these other monomers which can be copolymerized may be used. However, among these, the other monomer which can be copolymerized, -12-1293934 is desirably one or more selected from the group consisting of an aminated ethylene monomer and an unsaturated carboxylic acid alkyl ester monomer. By copolymerizing with an aminated ethylene monomer, it is improved in adhesion, chemical resistance, rigidity and dimensional stability. Further, it is copolymerized with an unsaturated carboxylic acid alkyl ester monomer to improve transparency, hardness and rigidity. It is preferred to co-polymerize the two together. The thermoplastic resin used in the present invention is one in which the diene rubber particles obtained by polymerizing a diene monomer are dispersed in the masterbatch resin. The ratio of the diene monomer in the rubber particles at this time is preferably 50% by weight or more, more preferably 80% by weight. /. the above. In the case of the diene monomer, for example, it may be ruthenium, 3-butadiene, isopropylene or the like, and one or more of them may be used. Among these, 1,3-butadiene which is excellent in performance and low in cost is desirably used. Specific polymers, for example, polybutadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), polyisopropylene rubber, etc., especially polybutadiene The rubber is an excellent resin which can provide low-temperature impact resistance and the like, and the cost is also low. Regarding the average particle diameter of the above rubber particles, although it is not particularly limited, it is preferably 〇. 〇 微米 Micron, more preferably 〇_〇 8~5 microns. The composition ratio of the thermoplastic resin to be used in the present invention is not particularly limited, but is desirably from 5 to 50% by weight of the diene rubber, and 10 to 90 parts by weight. /. The aromatic diene monomer and 10 to 90 parts by weight. /. The other monomers copolymerizable as described above are polymerized to form 1293934. Such a composition ratio is a ratio of each component in the thermoplastic resin which is not in the final molded article, for example, a diene is previously prepared in a predetermined amount of an aromatic diene monomer and other monomers copolymerizable. In the case where the rubber is modified, and further, the mixture is melted together with the copolymer of the additionally polymerized aromatic secondary storage monomer and the other monomer copolymerizable, the ratio of the total amount of the mixture is indicated. The content of the diene rubber is preferably from 5 to 50% by weight. When at less than 5 weight. /. In the case of the case, the impact resistance is insufficient, and therefore it is preferably at least 1% by weight. On the other hand, when it exceeds 50% by weight, the rigidity or formability may be lowered, so it is preferably 30% by weight or less, more preferably 20% by weight or less. Further, the content of the aromatic vinyl monomer-derived component is preferably from 10 to 90% by weight. In the case of less than 1% by weight, the rigidity or formability may be lowered, so it is preferably at least 20% by weight. When it exceeds 90% by weight, the impact resistance may be lowered, and it is preferably 80% by weight or less. In particular, in the case where transparency is required, it is preferably 50% by weight or less, more preferably 30% by weight or less. The content of other monomer-derived components copolymerizable is preferably from 10 to 90% by weight. It is more preferably 2% by weight or more and still more than 80% by weight. In particular, in the case where transparency is particularly required, the other monomer copolymerizable is preferably an unsaturated carboxylic acid alkyl ester monomer-derived component, and the content thereof is preferably 40 to 80% by weight. By this method, the refractive index difference -14 - 1293934 between the master batch resin and the rubber particles can be made small, and the entire resin can be made transparent. The method for producing the thermoplastic resin to be used in the present invention is not particularly limited, and it can be obtained by emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or the like. Made by law. However, among these, the diene rubber is a process of graft copolymerizing an aromatic vinyl monomer and another monomer copolymerizable, however, the dispersibility of the rubber particles, It is preferable from the viewpoint of the strength of the interface between the rubber particles and the master batch resin. When the diene rubber is modified, it may be graft-modified in an emulsion containing latex (latex), or may be graft-modified in a solution in which the rubber is dissolved. One of the ideal manufacturing methods is to copolymerize an aromatic vinyl monomer and other monomers copolymerizable in an emulsion in which diene rubber particles obtained by polymerizing two suspicion monomers are dispersed. A method in which a graft copolymerized resin, a further aromatic vinyl monomer, and another copolymerizable monomer are copolymerized and melted and mixed together. When the graft copolymerization is carried out in the emulsion, the rubber composition, the particle diameter, the sol content, and the like are easily controlled, and a high-performance resin excellent in transparency, impact resistance and moldability can be easily obtained. Further, the graft copolymerized resin particles synthesized in the emulsion are diluted by a copolymer obtained by another block (or solution) polymerization, whereby the amount of the metal salt derived from the emulsion can be reduced. 1293934 In the above manufacturing method, although various additives such as an emulsifier, a polymerization starting material, and a salting-out agent can be used in the emulsion polymerization process, in most cases, these are mostly metal salts, which are easily mixed into the final. Product problem. In the emulsion polymerization, it is necessary to use an amount equivalent to the emulsifier. However, most of these are alkali metal salts of higher fatty acids and alkali metal salts of sulfuric acid. Further, as the polymerization initiator in the emulsion polymerization, a peroxide or the like may be used. However, an emulsion initiator using an organic hydroperoxide may be used. In this case, an iron salt or the like is often used. Further, when the obtained graft copolymer resin particles are solidified after the emulsion polymerization, a high concentration of an alkali metal salt or an alkaline earth metal salt is often 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 emulsion polymerization, it is preferred to use an acid to solidify it, and an acid which can be used, for example, it may be hydrochloric acid. And sulfuric acid. at this time,. It does not matter if the auxiliary salt is used, but it is preferable to use no salt and to coagulate it only with acid. By doing so, it is possible to avoid the incorporation of metal salts in the solidification process. Further, in order to wash the conditions after solidification, it is preferred to increase not only the amount of washing water but also the number of washings. In particular, the washing water is preferably the same volume or more as the apparent volume of the graft-polymerized resin particles to be washed, and is preferably used in an amount of 2 times or more, more preferably 3 times or more. Further, it is preferred to carry out the washing-dehydrating step twice or more, and it is more preferable to carry out the washing three times or more repeatedly. In the general ABS resin manufacturing process, the cleaning-dehydration process is usually -16-1293934 without repeated operations. As described above, the graft polymerized resin particles after the emulsion polymerization are solidified using a small amount of acid, and sufficiently washed, and then melted and mixed with another block (or solution) polymerized copolymer. Reduce ash efficiently. The method of melt mixing is not particularly limited, and it may be mixed by a known kneading device such as an extruder, a Banbury mixer, a roll, or a kneader. At this time, it is possible to simultaneously mix with other components such as an antistatic agent. One of the other preferable production methods is a method in which a diene rubber obtained by polymerizing a secondary combustion monomer is dissolved in an aromatic vinyl monomer and another monomer which can be copolymerized, and then the aforementioned aromatic A method of polymerizing a vinyl monomer and other monomers copolymerizable therewith. In this case, a bulk polymerization method in which polymerization is carried out in a state in which no other solvent is contained, or a solution polymerization method in which polymerization is carried out in the presence of another solvent such as ethylbenzene may be employed, and any one may be used. According to these methods, the thermoplastic resin used in the present invention can be produced without passing through the emulsion polymerization process, and the residual amount of the metal salt derived from the emulsifier and the salting-out agent can be reduced. In such a manufacturing method, since it is not easy to control the particle diameter and composition of the rubber particles, compared with the manufacturing method having an emulsion polymerization process, transparency and impact resistance are insufficient in most cases, and thus It is certainly not a widely practiced manufacturing method. However, since the amount of residual metal salt can be reduced, it is a preferred method for the use of the invention of -17-1293934. The ash system of the thermoplastic resin used in the present invention is at 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 preferable. For example, in a semiconductor manufacturing process, as long as it is directly in contact with a wafer such as a wafer carrier, there is a case where it is a direct source of contamination of the wafer, and there is a case where metal ions are eluted in the treated water. Further, even in the case where the container is filled with the carrier so that the container does not directly contact the wafer, the worn dust may also adhere to the wafer or the carrier to have an adverse effect. In particular, in the semiconductor manufacturing process, when the metal ion is an impurity during the diffusion operation of the substance, the metal ion may diffuse into the circuit and the defective product rate may increase. The ash of the thermoplastic resin is preferably at 0. 18% by weight or less, more preferably at 0. 15% by weight or less. Further, in the case of the thermoplastic resin used in the present invention, the diene monomer used therein is preferably 1,3-butadiene, as described above. At this time, the content of 4_vinylcyclohexene of the thermoplastic resin is preferably 1 〇〇 ppm or less. 4-vinylcyclohexene is a cyclic dimer of 1,3-butadiene because it is mainly a by-product in the polymerization of a diene monomer. Because of the foul smell, it is an undesired product, and particularly in the case of a closed space operation such as a clean room, such malodor is particularly likely to cause problems. Further, in a closed space such as a clean room, since volatile organic compounds are likely to stay, they are a source of pollution and are not ideal. The 4-vinyl ring -18- 1293934 hexene content is preferably below 80 ppm, more preferably below 6 〇 ppm. In the case of emulsion polymerization, in order to reduce the enthalpy, the content of 3 丁 二 ' is preferably used to heat the emulsion after the emulsion polymerization, volatilize to remove the unreacted diene monomer, and simultaneously volatilize to remove the by-product heart. Ethylene cyclohexene. The heating method is preferably steam distillation, preferably at 6 〇C or more, more preferably at a temperature above 70 ° C, and preferably at a temperature of more than 1 , minutes, more preferably 30 minutes or more. Steam distillation operation. Further, it is preferred to enhance the washing conditions after solidification after the emulsion polymerization. At this time, the preferable washing conditions are as described above. Further, in the case of bulk polymerization or solution polymerization, it is preferred to reduce the content of 4-ethylenecyclohexene by strengthening the volatiles removal process. Specifically, after the end of the polymer, it is preferably 180. (The above, more preferably, the temperature is 200 ° C or higher, and the pressure is reduced to 1 Torr or less, and preferably 50 To "" or less, and unreacted monomers are removed, and 4-vinylcyclohexene is simultaneously removed. In the case where a solvent is used for the polymerization, although the solvent and 4-vinylcyclohexene are simultaneously removed, it is preferred to remove 4-ethylenecyclohexene with good efficiency. The thermoplastic resin used in the present invention may contain various kinds. In the specification of the present invention, the term "thermoplastic resin" includes a composition containing an additive. Among various additives, for example, an antistatic agent is contained because it can prevent the electrostatic breakdown of the semiconductor wafer, and It is preferably -1 to 993934 from the viewpoint of preventing adhesion of fine particles. Such an antistatic agent may, for example, be a cationic surfactant such as an alkylamine or a sulfate of a higher alcohol, Sulfate salt of an ethylene oxide adduct of a higher alcohol, a sulfate salt of an ethylene oxide adduct of an alkylphenol, an alkane sulfonate, an alkyl benzo sulfonate, an alkyl group a succinate salt, a salt of a naphthoic acid sulfone polycondensate, a phthalate salt of an ethylene oxide adduct of a higher alcohol, a phthalate salt of an ethylene oxide adduct of an alkyl phenol, an alkylphenol Anionic surfactants such as phthalate esters of ethylene oxide adducts, sorbitan esters of higher fatty acids, monoglyceryl ether esters of higher fatty acids, ethylene oxide adducts of monoglyceryl ethers of higher fatty acids, oxidation of higher alcohols Nonionic surfactants such as ethylene adducts, ethylene oxide adducts of higher fatty acids, ethylene oxide adducts of higher alcohols, oxime ethylene oxide adducts, alkylene oxide ethylene oxide adducts, etc. The alkyl diol, the polyalkyl diol copolymer, the polyether decylamine, the conductive carbon, etc., may be used alone or in combination of two or more. Among these, it is preferred to use a polyether ester. Because the polyether ester decylamine does not form a salt, there is no need to worry about eluting the salt. Moreover, 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 Can play for a long time Specific examples of the polyether ester decylamine, for example, will contain an aminocarboxylic acid having 6 or more carbon atoms, a lactone having 6 or more carbon atoms, and a diamine and a dicarboxylic acid. The obtained polyfluorene amine (A) obtained by extracting at least one of the polyfluorene-based compound (A1) having a carbon atom of 6 or more salts and the carboxy-carboxylic acid (A2) obtained by the -20-1293934 dicarboxylic acid (A2), a compound obtained by polycondensation of a polyether diol (B) formed of an ethylene oxide adduct of polyoxyalkylene glycol and/or a biphenyl ester, etc. Further, 'requires transparency In general, the polyetheresteramine is preferably treated to have the same refractive index as the thermoplastic resin used in the present invention. The refractive index of the polybutadiene is 1. 52. Since 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 the polyether ester decylamine is preferably 1 at room temperature. 4 8~ 1. 56, more preferably 1_50~1. 54, the most appropriate is 1. 51~1. 53. Further, if it is not required to be transparent, it is preferable to use conductive carbon as an antistatic agent. As described later, when an organic compound is used as an antistatic agent, it goes without saying that it is of course feared that it is thermally decomposed during molding. According to this, the conductive carbon such as graphite powder, carbon black, carbon fiber, or carbon nanotube is hardly decomposed at the temperature at the time of melt molding of the thermoplastic resin. Therefore, it is preferable to use conductive carbon particles as an antistatic agent for the purpose of contamination such as a volatile organic substance such as a clean room container. Further, the ratio of use of the above-mentioned static electricity prevention agent is not particularly limited. However, it is preferable to contain 1 to 30 parts by weight of the thermoplastic resin of the present invention depending on the physical property balance surface. /. . Further, the thermoplastic resin to be used in the present invention may be added with a known additive insofar as it does not impair the effects of the present invention. For example, an oxidation inhibitor, an ultraviolet absorber, and a -21-1293934 smoothing agent may be added as needed. , coloring agents, filling agents, etc. However, when it is difficult to produce a contaminated substance, it is preferable to keep the amount of such an additive to a minimum when considering the performance required for the clean room container of the present invention. The method of blending the above additives with an antistatic agent or the like is not particularly limited, and an extruder, a Banbury mixer, a roll, a kneader, or the like may be used, and may be used in combination. As described above, when the graft copolymerized resin particles and the resin obtained by copolymerization are melt-mixed, it is desirable to carry out the removal of volatiles in order to simultaneously remove the volatile components during melt mixing. deal with. The removal of the volatile component treatment method is, for example, the most appropriate method for performing the pressure reduction in a molten state. Specifically, it is preferred to use an extruder having a reduced pressure outlet for melt-kneading. The extruder can be a single-axis extruder or a two-axis extruder. Also, the exit can be set to a plurality of positions instead of only one location. At this time, the ideal melt kneading temperature is 160 to 220 °C. Further, by repeating such removal of the volatile matter, the content of the volatile component in the resin can be further reduced. For example, when melt-kneading is carried out using an extruder having a pressure-reducing outlet, it is preferred to repeatedly melt-knead the melt-kneaded plate-like compound. The melt flow rate (220 ° C, 10 kg load) of the thermoplastic resin used in the present invention is not particularly limited, but is usually 1 to 1 gram / 10 minutes. From the viewpoint of formability, it is preferably 5 -22 - 1293934 g / 10 minutes or more, and it is preferably 5 gram / 1 〇 minute or less from the viewpoint of strength. Further, in the case where the present invention is used for applications requiring internal visibility, the thermoplastic resin is preferably a transparent material. For example, a case like using a box containing a wafer carrier. In this case, the thermoplastic resin is preferably a resin having a haze of 20% or less at the time of injection molding having a thickness of 3 mm. By having a haze of 20% or less, it is not only easy to visually recognize the inside from the outside of the container, but also has a beautiful appearance. Further, for example, it is possible to perform production management by reading a wafer or the like attached to a carrier from the outside by a reading device. Further, if it is expressed in full light transmittance, it is preferably at least 70%, more preferably at least 80%. The thermoplastic resin obtained by this method is used to form the container for a clean room of the present invention. The molding method is not particularly limited, and various melt molding methods such as injection molding, extrusion molding, and melt blow molding can be employed. Further, it is also possible to perform secondary processing such as hot forming once the sheet or the like which has been subjected to extrusion molding. Among these, for example, in the case of a clean room container, since it is required to have a relatively complicated dimensional accuracy, it is preferable to perform molding by injection molding. The molding conditions at the time of injection molding are also not particularly limited, but it is preferred to form the drum set temperature to 22 CTC or less. Generally, when the ABS resin is injection molded, it is usually injection molded at a resin temperature of 230 ° C or higher. However, in the present invention, decomposition of the resin is expected to be minimized by 220 -23 to 1293934 ° C or less. limit. The melting time of the formed resin is usually not as long as possible. On the way, it is preferable to consider the formability and the forming speed to be sufficiently high; for the purpose of cleaning indoor use, not only the thermal decomposition during melting can occur. The amount of organic matter is important. It is preferred to reduce the possible forming temperature to the minimum forming temperature. The shape temperature differs depending on the composition of the resin and the melt flow rate, and is determined by factors. For example, increasing the proportion of the constituents of the unsaturated ester monomer in the resin can be easily made relatively low. The drum set temperature at the time of injection molding is preferably below, more preferably 20 CTC or less. Also, pass 1 60 °c or more. Further, the temperature of the molten resin at the time of injection molding also affects the thermal decomposition behavior of the additive in the resin. EXAMPLES The thermoplastic resin used in the container for clean room of the present invention contains an antistatic agent, and among them, a polyether ester oxime is preferably described above. At the time of melt molding, although it is a trace amount, the static electricity prevention agent is thermally decomposed. At this time, low-molecular-weight amines and guanamines which are formed by thermal decomposition at high temperature are formed (including an increase in amount. The amines and guanamines are dissolved in water to contaminate the semiconductor wafer through the treatment liquid, and more, due to the inclusion of such gas enthalpy In the semiconductor manufacturing process such as thermal diffusion treatment, there is a possibility that an alkaline substance such as an amine may be used, and therefore, it may be reduced in general temperature alone, and may be considered as a carboxylic acid. The temperature of the alkane to 2 1 0 ° C is often in the case of blending, such as a suitable amine, but in this case, the ester is easy to synthesize, producing ammonia from carbon, -24-1293934 hydrogen, The organic compound composed of oxygen is a more disgusting source. Therefore, in particular, when an inhibitor containing a nitrogen element as described above is used, it is preferred to form it at a low temperature as much as possible. The amount of the decomposed organic matter in the container for a clean room of the present invention formed in this manner is preferably as small as possible. Specifically, after the sample cut from the molded article is kept at 10 ° C for 10 minutes, the amount of organic gas generated in 10 minutes is preferably 600 ppm or less. It is ideally below 400, and more desirably below 300 p p m. When the amount of the decomposed organic substance is reduced to such a degree, the volatile component is effectively reduced in the production of the resin as described above, and at the same time, it is effectively formed as much as possible. The container for a clean room of the present invention is a container which can be used in a clean room, and is not particularly limited as to contain a raw material, an intermediate product or a product. For example, it is an ideal container for articles such as a semi-conductive board, a display device substrate, and a selected one of the recording medium substrates. The semiconductor substrate is, for example, an integrated circuit fabricated, a substrate for solar cell manufacturing, or the like. This material is not limited to what is represented by 矽. Further, the form may be a circular shape such as a wafer, or may be a form such as a solar cell, and a form in which the wafer circle is cut into a wafer, and there is no representative embodiment thereof. In the case of wafers contaminated with static electricity, the clock can be used as a low-temperature device, and the body-based body has a special image. Nearly -25- 1293934, the wafers have been gradually larger in diameter, and the size of the wafer containers has gradually increased. Therefore, it is possible to maintain and not damage the shape of the container having a large size, and it is desirable to use a resin excellent in rigidity and impact resistance. From this point of view, the container for clean room of the present invention is most desirable. Further, as the size becomes larger, the level of dimensional accuracy of the entire molded article becomes strict. Therefore, the container for a clean room of the present invention which can be molded with good dimensional accuracy is most preferable. Therefore, the container for a clean room of the present invention is preferably used for a tantalum wafer of 6 inches or more, and is preferably used for a tantalum wafer of 8 inches or more, and more preferably for a tantalum wafer of 300 mm or more. In this case, in the case of a container called a carrier in which a wafer is directly arranged, since the germanium wafer is in direct contact with the carrier, metal contamination is particularly likely to be a problem, and it is easy to cause staggered contamination through the processing liquid or the like. Therefore, it is preferable for such a carrier to be a container for a clean room of the present invention. In this case, it is particularly preferable to use a transparent resin which can be regarded as the inside. Further, since the volatile component is likely to be filled in the cell, it is preferable that the volatile component such as the odor component is the least contaminated. Therefore, even in the case of a container which is formed as one of a carrier and a case, it is preferable to use the container for a clean room of the present invention. The display device substrate is, for example, a substrate for manufacturing a liquid crystal display device, a substrate for manufacturing a plasma display device, a substrate for manufacturing an electroluminescence display device, or the like. A representative material of such substrates is glass 'other articles', for example, transparent resin or the like. In the case of the display device substrate of the present invention, it is preferable that the container for the clean room is used because the circuit for driving the pixel is present and the contamination due to the metal is abhorrent. Further, since the display device substrate is mostly extra large, it is preferable to use the clean room container of the present invention in the same manner as the above-described large-diameter silicon wafer. Further, the recording medium substrate is, for example, a hard disk substrate and a disk substrate. The material in the case of the hard disk substrate is represented by metal and glass, but is not particularly limited. Further, the material of the optical disk substrate is represented by a transparent plastic representing polycarbonate, but is not particularly limited. In the case of such recording media, although the composition of the recording film differs depending on the form of recording, since the recording density is drastically improved in recent years, even a small amount of pollutants may affect the performance, and thus the cleaning room of the present invention is used. The container is ideal. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in further detail by way of examples. [Synthesis Example 1] In a nitrogen-substituted polymerization reactor, 50 parts (solid matter) of polybutadiene latex (weight average particle diameter of 0. 3 //, sol content of 85 %) was placed. · 1 part B; (3⁄4 diamine tetraacetic acid sodium, 〇· 〇 硫酸 硫酸 硫酸 、 3 3 3 3 3 3 3 3 3 3 3 , , , , , , , , , , , , , , , , , , , , , , , , , , Nitrile, 12 parts of styrene, 35 parts of methyl methacrylate and 0. Two parts of cumene hydroperoxide were used to form a mixture of -27 to 1293934, and further polymerized at 60 ° C to obtain a graft copolymer emulsified latex. Then, using a latex meter with respect to 100 parts by weight (solid matter). After salting out 3 parts by weight of magnesium sulfate, 1.5 parts by volume of water of the graft copolymerized resin particles is added, and after dehydrating, washing, and drying, the graft copolymer resin particles are obtained. ). [Synthesis Example 2] The graft copolymerized resin particles were obtained in the same manner as in Synthesis Example 1 except that the steam distillation in the synthesis example 1 was carried out, and the solidification and washing processes were carried out. Namely, water vapor was blown into the graft copolymerized latex obtained after the polymerization to carry out steam evaporation for 1 hour. At this time, the temperature of the latex was 80 °c. After steam distillation, 1 part by weight is used as a coagulant to solidify, and further, graft copolymerized resin particles are added. After 5 times the volume of water and stirring, the dehydration washing operation was repeated three times. The graft copolymer resin particles (2) were obtained in the same manner as in the synthesis except the above. [Synthesis Example 3] 130 parts of pure water and hydrazine were placed in a nitrogen-substituted polymerization reactor. After 3 parts of potassium sulfate, the temperature was raised to 65 t under stirring. Thereafter, 1 part of acrylonitrile, 30 parts of styrene, 60 parts of methyl methacrylate and 0. 35 parts of t-month mixed monomer composed of thiol mercaptan and 30 parts of an aqueous emulsifier solution containing 2 parts of -28-1293934 heterogeneous potassium rosinate. Then, the polymerization system was heated to 70 ° C and aged for 2 hours to obtain a styrene polymer latex. Then, after salting out with 2.5 parts by weight of magnesium sulfate based on 100 parts by weight (solid matter) of the latex, 1 to 5 times by volume of water of the styrene-based polymer is added, and the mixture is dehydrated by stirring. After washing, it is further dried to obtain a styrene polymer (3). [Synthesis Example 4] A continuous polymerization apparatus formed using a fully-mixed reaction tank having a capacity of 20 liters was continuously supplied with 30 parts of styrene, 7 0 using a plunger pump at 13 kg/hr. Parts of methyl methacrylate, 10 parts by weight of ethyl benzene, hydrazine hydrazine 5 parts by weight of t-lauryl thiol, and 0. 015 parts by weight of a polymerization raw material composed of butyl butylperoxy (2-ethyl hexane ester) as a polymerization initiator, and polymerization temperature was adjusted to carry out polymerization. At this time, the polymerization temperature was 15 Torr, and the stirring rotation number of the reaction vessel was adjusted to 150 rpm. The polymerization was continued, and the polymerization liquid was continuously discharged from the reaction tank to the removal of the volatile matter, and then the styrene polymer (4) was obtained through an extruder. [Synthesis Example 5] A plunger flow type reaction tank having a capacity of 15 liters was used ("New Polymer Manufacturing Procedure Method" (Industrial Investigation Conference, Saeki Koji / Ogaki Shinji), page 185, section 7. The three types of reaction wells of the same type described in 5(b)) are shown as 10 segments C1/C0 = 0. 955) A continuous -29-1293934 polymerization unit with two 1-liter so-called complete mixing tanks to produce a thermoplastic resin. The plug flow type reaction tank constitutes a particle formation process, and the complete mixing tank of the first seat of the second reaction tank constitutes a particle diameter adjusting process, and the third reaction tank constitutes a post polymerization process. 22 parts by weight of acrylonitrile, 25 parts by weight of ethylbenzene, and 13 parts by weight of styrene-butadiene rubber (S3 10S manufactured by Nippon Co., Ltd.) were adjusted in the above-mentioned plug flow type reaction tank. . 2 parts by weight of lauryl mercaptan, hydrazine. 原料 5 parts by weight of butyl peroxy) 3,3,5-trimethylcyclohexane, and the raw material is continuously supplied to the stirring polymerization tank of 3 stages at 1 〇 kg/hr. In the apparatus, the polymerization of the monomer is carried out. Further, the first plug flow type reaction tank was set to 88 ° C, the second reaction tank was set to 125 ° C, and the third reaction tank was set to 140 °C. The polymerization liquid from the third reaction tank is supplied to a volatility removing device formed by a preheater (2 1 0 to 250 ° C) and a decompression chamber (40 T 〇rr), and then passed through an extruder. Thus, a thermoplastic resin (5) in which rubber particles are dispersed is obtained. The weight average particle diameter of the obtained rubber dispersed phase was 0. 5 microns. [Examples 1 to 5, Comparative Examples 1 to 4] The resins obtained in Synthesis Examples 1 to 5 and the following antistatic agents were mixed in accordance with the mixing ratios shown in Table ,, and 40 mm with an outlet was used. Biaxial extrusion ("TEX-44" manufactured by Nippon Steel Works Co., Ltd.) was melt-kneaded at 200 °C and cut to obtain nine tablets. That is to say, the nine granules were subjected to the removal of the volatile matter once. The antistatic agent used in -30-1293934 is "Brestar NC6321" manufactured by Sanyo Chemical Industry Co., Ltd. (polyether ester decylamine, refractive index is 彳. 516) and sodium lauryl benzosulfonate. The melt flow rate, ash content and 4-ethylenyl ring content of the obtained nine particles were measured in accordance with the methods described below. The measurement results are shown in Table 1. Using the obtained nine pellets, and using an injection molding machine of J450E-C5 manufactured by Nippon Steel Co., Ltd., the resin temperature at 200 ° C, the mold temperature was 50 ° C, the injection speed was 45 mm / sec, and the injection pressure was 1 600 kg/cm 2 was injection-molded to form a container as shown in Fig. 1. In each of Examples 1 to 5 and Comparative Examples 1 to 4, a molded article having a good appearance was obtained. However, in Examples 4 and 5, it was difficult to visually recognize the inside because it was cloudy. Further, the odor sensory evaluation was carried out in accordance with the method described below. The evaluation results are shown in Table 2. (1) Melt flow rate The melt flow rate (g/10 minutes) was measured based on AST M D-1 238. The measurement temperature is 2 2 (TC, the load is 10 kg. (2) The ash is accurately measured in the platinum crucible, and the measured dry weight is about 10 g of nine samples, and is placed in an electric cone furnace set in the ventilation chamber. After the uppering, the white gold crucible set to a temperature of 80 (TC electric furnace) was removed and left for 4 hours, and then the platinum was taken out in a desiccant and the weight was weighed, and the ash content (%) was calculated from the weight difference. (3) 4-vinylcyclohexene content - 3 1- 1293934 The nine samples of the sample were dissolved in dimethylformamide and manufactured by Harvey Parker Co., Ltd. with a flame ionization detector (FID). 8 9 Π Π type gas chromatograph to analyze the content of 4-vinylcyclohexene in the sample solution. Quantitatively prepared using a solution of 4-methylcyclohexene in a known concentration of dimethylformamide. (4) The total light transmittance was measured using a test piece of 3 mm using a reflection/refractive index meter H R-1 00 manufactured by Murakami Color Technology Co., Ltd. (5) Haze Use the same test piece as the total light transmittance, and use the village color (Response Ref. Ref. The static electricity prevention test piece is a test piece of 3 mm, and the state is adjusted for one month under the humidity of 23 ° C and 50% RH, and the surface intrinsic before and after the water washing treatment is measured by a super ohmmeter SN8210 manufactured by Toago Electronics Co., Ltd. Resistance 値 (Ω) (8) Odor-functional evaluation The container obtained by injection molding was placed in an open space for 24 hours at room temperature, and the upper and lower boxes were sealed and sealed at room temperature for 1 hour. Then, by 5 The scent-sensitive tester sniffed the odor level after opening the box on -32-1293934 to evaluate the odor function. The evaluation was based on the following criteria. 5 points: the odor is obvious and strong; 4 points: feels quite 3 points: feels odor; 2 points: feels slightly stinky; 1 point: does not feel stinky. 1293934 — 34丨 Surface inherent resistance 値 (after washing: Ω) Surface inherent resistance 値 (after washing: Ω) Impact resistance Sex (Mpa) smog (%) Line transmittance (%) 4-vinyl cyclohexene content (ppm) Ash (%) MFR of (g / 10 min) <Evaluation Results> Sodium lauryl benzosulfonate polyether ester guanamine rubber particle dispersion resin (5) Styrene polymer (4) Styrene polymer (3) Graft copolymer resin particles (2) Graft copolymerized resin particles (υ < blending ratio (parts by weight) > 00 X 〇CO X _A Ο 03 ho 00 σ> cn ο ο Κ) h〇cn cn 〇0J 〇Example X 〇σ> X ο 02 00 ND cn CO ο cn J ο -Λ. hJ h〇o 〇CO 〇ho X 〇cn X -Λ. Ο ΓΟ ΟΙ οι 00 σ> cn ο ο -1. Κ) KD ho VI 〇00 〇CO X -λ 〇05 -νΐ X -λ. Ο 05 CJ ο CO cn cn ο ο ο ο -JL ro 1 00 X -X 〇C0 ΟΙ X -Λ. ο 00 C0 αι 扛ο cn ο ο ο ο -Α _^ cn 1 00 cn X 〇 σ> 4^ X __Λ. Ο 05 0J 00 00 300 ο κ> ΟΊ M ro -vl 〇C0 ο Comparative example ro X -χ ο CO Κ) X ο CO ο αι 00 CO 300 ο ro ΟΊ M 00 cn 〇CO ο Ν) ΟΊ X _Χ Ο ΙΟ σι X _χ Ο ΓΟ ΓΟ U1 ho 00 ro ο 0.001 CO o 00 100 LO 00 X -X Ο CT) 00 X _X Ο σ> _X CD ο 0.001 K) 1 00 1293934 -35丨Evaluation Average Tester v Tester IV Tester Π Tester π Tester I ND Ren tUEJ 05 g? Μ S? ro 沣ho §? 〇〇turn S? Example K) 7 g? CO m CO \\m Π -γ κ> B? ro B? OJ iUS 鎞ro N> Ο) m nr CO ho CO ho rus s n? CO g? 03 to m «Jk tUJZI D? -Jk g? M n? g? tUS D? ro ho g? g? cn 4.4 points cn §? m rhr Σι S? vm Or Comparative example σι ο g? cn g? σι tuss D? cn g? cn m Ut Ol μ _1 g? _^ g? —X m Ώ-rh〇m nr hO vm Dp _1 §? CO — XN) g? _x Π-Γ _X m rhr Λ_Χ m Ur _x m Ehr ho View Dt 1293934 It can be understood from the above results that in the production of graft copolymerized copolymerized resin particles, in addition to the use of acid to solidify and strengthen the cleaning In the operation, Examples 1 to 3 in which the resin particles obtained by this method were mixed with the solution-polymerized styrene-based polymer to produce a thermoplastic resin showed low ash. Further, Examples 4 and 5 which synthesized the thermoplastic resin in which the rubber particles were dispersed without the emulsion polymerization process also showed low ash. On the other hand, in Comparative Examples 1 and 2, which have salting out using a metal salt and performing only a general washing operation, the ash content becomes high. Further, in the case of producing a graft copolymerized copolymerized resin particle, a steam distillation operation is carried out, and the resin particles obtained in this manner are mixed with a solution-polymerized styrene polymer to produce a thermoplastic resin. 3. Examples 4 and 5, in which the content of 4-vinylcyclohexene is lowered, and the thermoplastic resin having odor-functionally dispersed rubber particles is dispersed, and the content of 4-vinylcyclohexene is also lowered, and the odor function is evaluated. The result is also good. Further, in Examples 1 and 5 in which polyether ester decylamine was used as an antistatic agent, it was possible to obtain an antistatic effect which was excellent before and after washing. However, Examples 2 and 4 which did not use an antistatic agent were used before and after washing. The surface specific resistance 値 becomes high, so that the static electricity prevention is insufficient. In Example 3, which uses sodium lauryl benzosulfonate as an antistatic agent, although the surface specific resistance 値 before and after washing is lowered, the surface specific resistance 洗 after washing is high, and the static electricity prevention effect is obtained. After the continuation of -36- 1293934, the inherent resistance of the surface becomes high, which is insufficient in terms of the persistence characteristics of the static electricity prevention effect. Further, in Comparative Examples 3 and 4 containing no diene rubber particles, the impact resistance was deteriorated. [Examples 6 to 9] (Impact of molding temperature) The same thermoplastic resin as that used in Example 1 was used, and an injection molding machine of J450E-C5 manufactured by Nippon Steel Co., Ltd. was used, as shown in Table 3. The drum was set to a temperature of 50 ° C, an injection speed of 45 mm / sec, and an injection pressure of 1,600 kg / cm 2 for injection molding to prepare a container as shown in Fig. 1. With respect to these containers, the evaluation of the formability and the amount of organic matter was carried out in accordance with the method described below. The results are shown in Table 3. (9) Formability The chargeability of the resin was observed. When the resin was completely filled in the shape of the container, it was marked as 〇, and when the resin could not be completely filled in the shape of the container, it was recorded as X. (1〇) Decomposition of organic matter A sample of 10 mg was taken from the molded product, and after holding at 150 ° C for 1 〇 minutes, the amount of organic gas generated in 10 minutes was measured, and the apparatus was measured using Havert Park. The company has a G-1 800 A gas chromatograph. Calculate the amount of organic gas converted to styrene. -37 - 1293934 丨38丨=1. Number of volatility removal by ventilation (times) Volume of organic gas (ppm) Formability bf Μ Injection speed (mm/s) Mold temperature (°C) Roller set temperature (°C) 700 〇1600 4^ 〇1 cn ο 240 )Β|Spectrum G) 500 〇1600 cn cn ο 220 —λ Example 7 400 〇1600 Ren cn cn ο 200 Μ 00 350 X 1600 Ren cn cn ο 1 80 CD 300 〇 1600 仁 α αι ο 200 实施 Example 1 〇1 50 〇1600 〇1 cn ο 200 Example 11 1293934 It can be understood from the above results that as the forming temperature is lowered, the total amount of gas to be removed is reduced. This fact shows that the amount of decomposition of the organic compound at the time of injection molding increases as the injection temperature rises. When the temperature of the molten resin at the time of injection molding is 1 80 °C, the moldability is lowered, but a good molded product can be obtained at 200 °C. Further, it is understood that the amount of the organic volatile component in the molded article can be greatly reduced by repeating the operation of removing the volatile matter after the compound. [Industrial Applicability] The container for clean room of the present invention is excellent in dimensional accuracy during molding, smoothness of surface of a molded article, rigidity, impact resistance, and the like, and resin cost is relatively low, and ash is also Since it is less likely to cause a source of contamination due to metal ions, it has excellent performance as a container used in a clean room. Therefore, there are particularly containers for use as a semiconductor substrate, a display device substrate, and a recording medium substrate. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an exploded perspective view showing the entire structure of a container which is not formed in the embodiment of the present invention. The figures show: 1 for the container, 2 for the upper box, and 3 for the lower box. [Component Symbol Comparison Table] 1 Container 2 Upper Box 3 Lower Box