572901572901
(發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明) (一） 發明所屬之技術領域 本發明關於中空成形體用聚乙嫌系樹脂及由該樹脂所成 之中空成形體。更詳而言之，本發明關於中空成形體用聚 乙烯系樹脂，其能製備具有優良的軸向彎曲強度、耐環境 負荷（瓶ESCR)及耐落下衝擊性而且具有優良的外觀之中空 成形體，以及關於及由該樹脂所成之中空成形體。 (二） 先前技術 向來，在中空成形體中，從資源保護及廢棄物量削減的 觀點看，必須減少樹脂的使用量。 然而，在利用於例如洗劑等的容器時，聚乙烯，尤其高 密度聚乙烯所成的中空成形體，由於在塡充內容液和輸送 時必須確保軸向彎曲強度，故增加容器的壁厚，而使得樹 脂的用量傾向於變大。爲了使容器的壁厚變薄、減少樹脂 使用量而仍確保軸向彎曲強度，使用密度高的高剛性聚乙 烯樹脂係有效的。然而，在使用密度95 7 kg/m3以上的聚 乙烯材料當作具有優良軸向彎曲強度的瓶子之情況中，當 貯存內容液如洗劑或柔軟材、漂白劑時，由於瓶ESCR的 不足，而容易發生龜裂，實用化係困難地。 因此，期望一種中空成形體用聚乙烯系樹脂的出現’其 由能製備高密度、壁薄而軸向彎曲強度優良且耐環境應力 龜裂優良的中空成形體之高密度聚乙烯系樹脂所構成’以 572901 及一種由該樹脂所成的中空成形體之出現。 (三）發明內容 發明所欲解決的問頴 本發明之目的爲解決上述先前技術的問題，而提供一種 高密度、優良的軸向彎曲強度、優良的瓶ESCR且難以發 生環境應力龜裂的中空成形體用聚乙烯系樹脂及由該樹脂 所成之中空成形體 解決問穎的丰段 本發明所關於的中空成形體用聚乙烯系樹脂之特徵在於 其之熔體流速（MFR; JIS K7210，190。(：，2.16公斤荷重，單 位爲克/10分鐘）係0.1〜2.0，密度（JIS K6922-2，測定樣品 爲MFR計股束，在沸水中退火30分鐘，單位爲kg/m3)係 在95 7〜967的範圍內，而且Mz (Z平均分子量）滿足式Mz ^ -4x1 05 logMFR + 1.2X106 〇 上述聚乙烯系樹脂較佳爲一種聚乙烯，其在21.6公斤荷 重下測定的熔體流速（MFR2 1.6)値除以在2.16公斤荷重下 測定的熔體流速（MFR2.16)値所得之値 [(MFR21.6)/(MFR2.16)]較佳爲 200 以下。 又，本發明所關於的聚乙烯中空成形體含有至少一層由 上述中空成形體用聚乙烯系樹脂所成之層，可適用於貯存 洗劑、漂白劑或柔軟劑等。 發明的實施形態 以上具體說明本發明所關於的中空成形體用聚乙烯系樹 脂以及使用該樹脂所成之中空成形體。 -8- 572901 生._空成形體用聚乙烯系樹脂 本發明所關於的中空成形體用聚乙烯系樹脂之熔體流速 (MFR; JIS K7210，190°C，2.16 公斤荷重，單位爲克/10 分 鐘）係在〇·1〜2.0克/10分鐘的範圍內，較佳在0.1〜1.0 克/10 分鐘的範圍內，更佳在0.1〜0.7 克/10分鐘的範圍內。若 熔體流速在該範圍內，則成形性較佳。 又，其之密度（JIS K6922-2，測定樣品爲MFR計股束，在 沸水中退火30分鐘，單位爲1^/1113)係在95 7〜967 1^/1113的 範圍內，較佳在 95 7〜963 kg/m3的範圍內。若密度在該範 圍內，則軸向彎曲強度較佳。 再者’本發明所關於的中空成形體用聚乙烯系樹脂之特 徵在於使用GPC(凝膠滲透層析術）所測定的Mz(Z平均分子 量）滿足式Mz^-4xl05 logMFR + 1·2χ106。Mz滿足該範圍 的意思爲就平均分子量的比率而言，有高分子量成分的存 在。若Μ z在該範圍內，則瓶e S C R較佳。 Μζ(Ζ平均分子量）係使歐塔司（音譯）公司製的GPC-150 如下來測定。 分離管柱爲2支東曹（股）製TSK GMH 6ΗΤ和2支TSK GMH6HTL，合計4支，管柱溫度爲14(TC，移動相使用鄰 二氯苯（和光純藥工業（股）製），抗氧化劑使用0.025重量％ 的BHT(3,5-二第三丁基羥基甲苯）（武田藥品工業（股）製）， 以每分鐘1 ·〇毫升移動，試料濃度爲〇·；!重量〇/。，試料注入 量爲500微升，檢出器爲微差折射計。使用東曹（股）製的 標準聚苯乙烯藉由標準法來校正管柱，換算成聚苯乙烯^ -9- 572901 又’藉由使上述聚乙燦系樹脂之在21.6公斤荷重下測定 的熔體流速（MFR21.6)與在2.16公斤荷重下測定的熔體流 速（MFR2.16)之比値[(MFR21.6)/(MFR2.16)]—般在 200 以 下，較佳在190〜30，更佳在180〜40，而能得到充分的衝擊 強度，尤其落下強度。 本發明所使用的聚乙烯系樹脂爲具有上述MFR、密度和 Mz之關係式的高密度聚乙烯，不僅乙烯均聚物，而且可使 用乙烯與少量的α-烯烴之共聚合，例如與1 〇莫耳％以下的 丙烯、1-丁烯、1-戊烯、3-甲基-1-丁烯、1-己烯、3-甲基-1-戊烯、4-甲基-1-戊烯等的α-烯烴，而成的乙烯·α-烯烴共聚 物。可單獨或組合2兩種以下來使用該些α-烯烴。 具有上述物性的高密度聚乙烯係可藉由齊格勒觸媒或金 屬茂觸媒等，以低壓法或菲利浦法等的中壓法，聚合乙烯 或乙烯與碳原子數3〜20的α-烯烴而被調整。 在本發明中，乙烯與α-烯烴的共聚合係在氣相或漿體狀 的液相中或在溶液中進行。就漿體聚合而言，惰性烴可以 當作溶劑，烯烴本身亦可以當作溶劑。 於進行漿體聚合法或溶液聚合時，聚合溫度通常在-5 0〜2 5 0 °C的範圍內，於進行氣相聚合法時，聚合溫度通常 在0〜120°C的範圍內，較佳在20〜100°C的範圍內。聚合壓 力通常在常壓至lOOatm的加壓條件下，聚合反應係可以由 分批式、半連續式、連續式中任一方式來進行。再者，亦 可以將聚合反應分成反應條件不同的2段以上來進行，包 括預備聚合、單段、多段皆可加速聚合反應。 -10- 572901 由於Mz係以高分子量成分影響大的平均分子量算出法 所得到’雖然有高分子量的存在但流動性係高的，可達成 MFR和Mz的目標範圍。具體地，若分子量分佈爲廣時， 由於有高分子量成分的存在，而可能達成申請專利範圍中 MFR和Mz的範圍關係。又，爲了製造分子量分佈廣且高 分子量成分存在的聚乙烯，可以進行多段聚合（連續使用二 段聚合、三段聚合等的反應器來連續製造分子量•密度不同 的聚乙烯之方式）或熔融摻合或倂用多段聚合與熔融摻合等 的方式，藉由摻合兩種以上的低分子量聚乙烯和高分子量 聚乙烯，而使Mz和MFR在目標範圍內。 又，於本發明的聚乙烯系樹脂中摻合以高壓法所製造的 聚乙烯，亦可以達成上述物性。於該情況中，使用密度 9 10〜9 3 5 kg/m3程度的高壓法聚乙烯。可使用的本發明之聚 乙烯系樹脂與高壓法聚乙烯的重量比通常爲1〇〇〜65/0〜35 , 較佳100〜8 0/0〜20。從成形性的觀點看，在該範圍內的高 壓法聚乙烯係較宜的。 又’在上述聚乙烯系樹脂或聚乙烯系樹脂組成物中，於 不會損害中空成形體之物性的範圍內，可以配合各種添加 劑。該添加劑的具體例子爲塡充劑、耐候安定劑、耐熱安 定劑、抗靜電劑、防滑劑、防霧劑、滑劑 '顏料、染料、 核劑、可塑劑、阻燃劑、鹽酸吸收劑等。 虫空成形體 本發明所關於的中空成形體係由上述聚乙烯系樹脂或聚 乙烯系樹脂組成物所形成。本發明所關於的中空成形體可 -11- 572901 以單層容器狀地由單層形成，而且亦可以多層容器狀地由 2層以上之層形成。 例如在由2層形成多層容器的情況中，一層由上述本發 明所較佳使用的聚乙烯系樹脂來形成，而另一層係由與該 聚乙烯系樹脂不同的樹脂來形成，或由上述本發明所較佳 使用的聚乙烯系樹脂來形成，一層可由具有與所用的聚乙 烯系樹脂之物性不同聚乙烯系樹脂來形成。 上述不同的樹脂例如爲聚醯胺（尼龍6、尼龍66、尼龍12、 共聚合尼龍等）、乙烯·乙烯醇共聚物、聚酯（聚對酞酸乙二 酯等）、改質聚烯烴等。 本發明所關於中空成形體可由習知的中空成形（吹塑成形） 法製得。在吹塑成形法中有各種方法，大致區分爲擠壓吹 塑法、2段吹塑成形法、射出成形法。於本發明中，較宜 採用擠壓吹塑法。 上述所製備的中空成形體係適用於漂白劑容器、洗劑容 器、漂白器用容器等的用途，例如適合作爲化粧品、柔軟 整理劑、洗髮精、潤濕精、處理劑等所使用的家庭用•業務 用之界面活性劑用容器或漂白劑用容器。 發明的效果 本發明所關於的第一種中空成形體用聚乙烯系樹脂之特 徵爲其之熔體流速（MFR; JIS K72 1 0, 1 90°C，2.16公斤荷重， 單位爲克/10分鐘）係〇·1〜2.0，密度（JIS K6922-2，測定樣 品爲MFR計股束，在沸水中退火30分鐘，單位爲kg/m3) 係在957〜967的範圍內，而且使用GPC(凝膠滲透層析術） -12- 572901 所測定的Mz (Z平均分子量）滿足式Mzg-4xl05 logMFR + 1· 2x1 Ο6，即使爲薄壁化的容器也能具有充分的軸向彎曲強 度和耐環境應力龜裂性。 又，本發明所關於的中空成形體用聚乙烯系樹脂之根據 JIS Κ7210在190°C於21.6公斤荷重下所測定的熔體流速 (MFR21.6)値與於 2.16公斤荷重下所測定的熔體流速 (MFR2.16)値的比値[(MFR21.6)/(MFR2.16)]在 200 以下時， 落下強度亦優良。 本發明所關於的中空成形體用聚乙烯系樹脂及中空成形 體係適用於洗劑、洗髮精、潤濕精、漂白劑、柔軟整理劑、 化粧品、蠟、食用油、沙拉醬、芥末醬等的容器、燃料桶、 工業藥品罐、圓筒罐、貯水槽等的用途。 (四）竇施方式 以下藉由實施例來說明本發明，惟本發明完全不受限於 該些實施例。 又，熔體流速（MFR)、密度及Mz(Z平均分子量）、拉伸 衝擊強度及耐環境應力龜裂F50値係以下述方法爲依據來 測定。 MFR: JIS K7 210，190°C，2·16 公斤荷重 密度：JIS Κ6922-2,測定樣品爲MFR計股束，在沸水 中退火3 0分鐘 Μζ:使用沃答斯公司製GPC-150，如下測定。 分離管柱爲2支東曹（股）製TSK GMH 6ΗΤ和2支TSK GMH6HTL，合計4支，管柱溫度爲i4〇°c，移動相使用鄰 -13- 572901 二氯苯（和光純藥工業（股）製），抗氧化劑使用〇·〇25重量％ 的BHT(3,5-二第三丁基羥基甲苯）（武田藥品工業（股）製）， 以每分鐘1 · 〇毫升移動，試料濃度爲0 · 1重量％，試料注入 量爲500微升，檢出器爲微差折射計。使用東曹（股）製的 標準聚苯乙烯藉由標準法來校正管柱，換算成聚苯乙烯。 拉伸衝擊強度： 以JIS K7160爲依據，使用JIS K7160第4型的試驗片 來測定。 耐環境應力龜裂F50値：以ASTM D1693 B法爲依據， 以安塔若克司C〇63 0當作界面活性劑，以10%水溶液來測 定。 實施例丄 於乙烯和1-丁烯的共存下使用觸媒，藉由多段聚合來製 造2.16公斤荷重下的MFR爲0.8克/10分鐘、21·6公斤荷 重下的MFR爲80克/10分鐘且密度爲9 5 9kg/m3的聚乙烯， 同樣地藉由多段聚合來製造2.16公斤荷重下的MFR爲0.〇4 克/10分鐘、21.6公斤荷重下的MFR爲7.4克/10分鐘且密 度爲959kg/m3的聚乙烯。使上述兩種聚乙烯以80:20的比 例熔融摻合。所熔融摻合的聚乙烯之2.16公斤荷重下的 MFR爲0·41克/10分鐘，21.6公斤荷重下的MFR爲50克/10 分鐘，密度爲959kg/m3，GPC所測定的Μζ爲16.7Χ105。 又，拉伸衝擊強度爲130kJ/m2，耐環境應力龜裂F50値 爲3 0 0小時。其結果記載於表1中。 <單層中空成形體之成形條件> -14- 572901 接著，使用擠壓吹塑成形機（日本製鋼（股）製，型號： JEB-15)，在聚乙烯的成形溫度：20(TC、樹脂擠出量：50 公斤/小時、模具溫度：20 °C的成形條件下，將該聚乙烯吹 塑成形，而得到內容量780毫升、重量25克和35克的圓 筒瓶（單層中空成形體），以及內容量2.5升、重量130克的 附把手之瓶（單層中空成形體）。 <單層中空成形體的重複落下試驗法> 依照下述方法來對上述所得到的瓶子進行重複落下試 驗。其結果係示於表1中。 使內容量780毫升、重量25克的單層瓶裝滿水，使該瓶 豎立著而在〇°C的環境下以一定的高度落下，最多重複1〇 次。藉由落下試驗，測量水由裂縫漏出外部時的重複落下 次數。重複該試驗1 0次，以測定瓶子形成裂縫時的平均落 下次數。瓶子落下的床係使用2吋厚的鐵板水平放置於混 凝土的床上者。 <單層中空成形體的軸向彎曲強度試驗法> 使用英特龍萬能試驗機，以每分鐘15mm，在30 °C試驗 溫度對內容量780毫升、重量35克的單層瓶作壓縮，所得 到的最大強度當作軸向彎曲強度。其結果記載於表丨中。 <單層中空成形體的瓶ESCR試驗法> 於內容量780毫升、重量35克的圓筒瓶中塡充78 cc下 述內容液，於內容量2·5公升、重量130克的附把手之瓶 中，塡充250cc下述內容液，然後密閉，於65艺保管，觀 察瓶子產生裂縫時的時間。所測定的瓶子之η數各爲1 〇支， -15- 572901 試驗開始後，記錄第1支瓶子產生裂縫時的時間。其結果 δ己載於表1中。 氯系漂白劑：花王（股）製起津亥達 氧系漂白劑：獅王（股）製特馬那西漂白劑 柔軟劑：花王（股）製海米庫 洗髮精：資生堂（股）製斯巴買魯得洗髮精 <3種五層中空成形體成形法及瓶ESCR試驗法> 又，使用擠壓吹塑成形機（日本製鋼（股）製，型號：〗EB-105PC)，將該聚乙烯吹塑成形，成形溫度：20(TC，樹脂擠 出量：10公斤/小時，模具溫度：20 °C，而得到內容量500 毫升、重量25克的圓筒瓶。 各層的厚度構成比爲，聚乙烯：黏著樹脂：乙烯•乙烯醇共 聚物：黏著樹脂：聚乙烯=41·· 3:2 :3:41。而且，黏著樹脂係使 用三井化學（股）製的阿德馬NB508，乙烯•乙烯醇共聚物係 使用可樂麗（股）製的艾巴魯F101B。 於所得到的瓶子中塡充50cc氯系漂白劑（花王（股）製起 津亥達），然後密閉，於65 °C保管，觀察瓶子產生裂縫時 的時間。所測定的瓶子之η數各爲1 〇支，試驗開始後，記 錄第1支瓶子產生裂縫時的時間。其結果記載於表1中。 <2種二層中空成形體成形法及瓶ESCR試驗法> 又，使用擠壓吹塑成形機（卜拉可（股）製，型號：卜拉可-3Β-50-4 0)，將該聚乙烯吹塑成形，成形溫度：20〇°C，樹 脂擠出量：8公斤/小時’模具溫度：2 0 °C，而得到內容纛 1000毫升、重量40克的圓筒瓶。外層爲聚乙烯，內層爲 -16- 572901 單層中空成形品粉碎物，各層的厚度構成比爲外層：內層 =80:20 。 於所得到的瓶子中塡充100CC氯系漂白劑（花王（股）製起 津亥達），然後密閉，於65 °c保管，觀察瓶子產生裂縫時 的時間。所測定的瓶子之η數各爲1 0支’試驗開始後，記 錄第1支瓶子產生裂縫時的時間。其結果記載於表1中。 竇施例2 使用MFR2.16公斤爲〇·29克/10分鐘、MFR2 1.6公斤爲 39克/10分鐘、密度爲9 59kg/m3、Μζ爲16.0Χ105、拉伸衝 擊強度爲170kJ/m2的聚乙烯來代替實施例1的聚乙烯，以 外與實施例1同樣地進行檢討。其結果記載於表1中。 實施例3 不用熔融摻合，而使用藉由多段聚合所連續生產的低子 量和高分子量成分所調整的MFR2.16公斤爲0.38克/10分 鐘、MFR2 1.6公斤爲57克/10分鐘、密度爲9 5 9kg/m3、Μζ 爲18.7Χ105、拉伸衝擊強度爲ll〇kJ/m2的聚乙烯來代替實 施例1的聚乙烯，以外與實施例1同樣地進行檢討。其結 果記載於表1中。 實施例4 使用MFR2.16公斤爲0.16克/10分鐘、MFR21.6公斤爲 25克/10分鐘、密度爲95 9kg/m3、Μζ爲20·〇χ1〇5、拉伸衝 擊強度爲22〇k J/m2的聚乙烯來代替實施例1的聚乙烯，以 外與實施例1同樣地進行檢討。其結果記載於表1中。 實施例5 -17- 572901 使用MFR2.16公斤爲0.49克/10分鐘、MFR21.6公斤爲 56克/10分鐘、密度爲960kg/m3、Mz爲15·4χ105、拉伸衝 擊強度爲120kJ/m2的聚乙烯來代替實施例i的聚乙烯，以 外與實施例1同樣地進行檢討。其結果記載於表1中。 實施例6 使用MFR2.16公斤爲0.29克/10分鐘、MFR21.6公斤爲 30克/10分鐘、密度爲961kg/m3、Mz爲16·0χ105、拉伸衝 擊強度爲1 80kJ/m2的聚乙烯來代替實施例！的聚乙烯，以 外與實施例1同樣地進行檢討。其結果記載於表1中。 比較例1 使用MFR2.16公斤爲0.36克/10分鐘、MFR21.6公斤爲 35克/10分鐘、密度爲955kg/m3、Mz爲12·1χ1〇5、拉伸衝 擊強度爲210kJ/m2的聚乙烯來代替實施例！的聚乙烯，以 外與實施例1同樣地進行檢討。其結果記載於表1中。 比較例2 使用MFR2.16公斤爲0.36克/10分鐘、MFR21.6公斤爲 35克/10分鐘、密度爲95 9kg/m3、Mz爲12·5χ105、拉伸衝 擊強度爲200kJ/m2的聚乙烯來代替實施例i的聚乙烯，以 外與實施例1同樣地進行檢討。其結果記載於表1中。 比較例3 使用MFR2.16公斤爲0.40克/10分鐘、]VIFR21.6公斤爲 84克/10分鐘、密度爲959kg/m3、Mz爲20·1χΐ〇5、拉伸衝 擊強度爲80kJ/m2的聚乙烯來代替實施例1的聚乙烯，以 外與實施例1同樣地進行檢討。其結果記載於表1中。 -18- 572901 鎰 *n o 丄1 叫 -Η On X 1—< 5 O O O z$ 〇 〇 〇 〇 ο ζ$ ο z$ ο AJ 〇 On s m s CN s CN s o »n 〇 〇 *n 〇 yr\ ο «ο ο Ό ο m *Λ o m V—· X X O uo 00 o o o 〇 〇 〇 -LJ 〇 〇\ <N •-H cn iTi ro 卜 On s v〇 o 1—^ (Ν <N CO 〇 寸 g — *Λ *r\ 〇 叫 -Μ 叫 -Η -Η f—< X X Ξί Ξ$ 3 ζ$ ν〇 to —· 00 o Csl o o 〇 〇 ο 〇 ο Ο ο d os cs m m 卜 ON CN o m 〇 ο m 〇 in ο Ο ο m *r\ «Λ 〇 -H 丄] -Η Μ Μ -Μ X X ζ$ 3 ζ$ 辑 u 0.29 v〇 as 〇 CS 寸· 〇 CO CO o CO 〇 00 卜 CN O o 〇 〇 ο ο Ό ο ο wo ο ο Ό ο ο »η ο ο ΙΛ «Λ Ο X •H Μ 丄I Μ X 3 ζ$ 3 ζ$ 習 u 0.49 o VO a\ 寸 CN cn v〇 寸 s cn S as tn 〇 wo CN o 〇 〇 Ο Ο »η ο ο yrs ο ο ΙΟ ο ο V-» ο ο 寸 «Λ *n 〇 -H -Η -Μ 丄I X X z$ ζ$ 3 3 3 3 辑 Os o (N KO o o 〇 o 〇 ο ο ο ο ο 〇 ^r\ On o CN cs in ΓΟ CN CN oo o 〇 «〇 ο ο ο »〇 ο 1/Ί ο CO *Λ νΐ o -H -Η -Η -Η -Η 1—^ X X 3 3 3 ο ο Ό 3 Ξ$ 辑 K 0.38 ON in ON 卜 00 Γ- γο 卜 uo o cn O <N o vn CO O o ir> 〇 〇 ο ο «τ> ο ο ο ο ο ο (N •Λ o 丄i 叫 -Η -Η -Η X X z$ Ξ$ ο ζ$ Ξ$ ο Ξ$ ο 〇\ 04 On 〇 <N 寸 〇 o o o 〇 ο ο U 〇 i〇 〇\ vd 寸 ON m m m 卜 卜 o o 〇 »〇 ο »τ» ο ο Ό ο ο tr) — <Λ *Λ o -H 丄1 X X z$ ζί ζ$ U 0.41 a\ ON 卜 m 〇 wo CN CN 〇 o 00 v〇 o 〇 o »n 〇 〇 »η ο ο »τ> Ο Ο »η ο ο ο ο ο ο *Τ) « * Φ： cs 〇 '^ "s w 、 6 、 篮 s 酙 1 1 1 2 七 七 七 七 七 七 七 七 七 JJ ifrml Pn 眩 /^\ 蘅 /^N 蕨 m s v〇 ΌΙ (^ ΊΉ 聽 o \y ^1? X CN ω味 w條 W繇 ω W ω i{l 1S ^ /—Ν — <N Uh o 错祕 镇铋 镇垢 m 蘅 豳蘅 袋*cn ilmil Pfl + itmil W 辁 *01 眩 u S 、 i 装 啦 ΓΛ+τ 鰹柴 鰹璨 φβ NO, ϋ柴 畔 tT/k 聽忙 链離 链_ Uh 2 Jmil P*1 m m « 柴亦 辁5 袋姊 染·· 创味 &0 « 腔 m m 1ge 1ge 1ge 1ge 發m CN 〇 »Λ 〇 CN v〇 CN 租 歉 m, w te 戰 m m » £ 别Μ €-S 心 2 2¾1 _装 od m X tL( Οίί 侄 t： 卜 m _诞 ，ι mm U娣 酬,-ρ. s B s 寸 κ S S s m * nut國 αΐπτ w 酹§ 酹® «-Β 螂Sen 7：^ E <N w 〇\(Explanation of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments and the drawings are briefly explained) (1) The technical field to which the invention belongs The present invention relates to a polyethylene resin for hollow formed bodies and the resin The formed hollow body. More specifically, the present invention relates to a polyethylene-based resin for a hollow formed body, which can produce a hollow formed body having excellent axial bending strength, environmental load resistance (bottle ESCR) and drop impact resistance, and excellent appearance. , And about and formed from this resin. (2) Prior art Conventionally, in the hollow formed body, it is necessary to reduce the amount of resin used in terms of resource conservation and waste reduction. However, when used in containers such as lotions, the hollow formed body made of polyethylene, especially high-density polyethylene, needs to ensure the axial bending strength when filling the liquid and transporting it, so the wall thickness of the container is increased. , And the amount of resin tends to become larger. In order to reduce the wall thickness of the container and reduce the amount of resin used while still ensuring the axial bending strength, it is effective to use a high-rigidity polyethylene resin with a high density. However, in the case of using a polyethylene material having a density of 95 7 kg / m3 or more as a bottle having excellent axial bending strength, when storing a content liquid such as a lotion or a soft material or a bleach, due to the lack of ESCR in the bottle, However, cracks easily occur, and practical applications are difficult. Therefore, the appearance of a polyethylene-based resin for a hollow molded body is expected to be formed of a high-density polyethylene-based resin capable of producing a hollow molded body having high density, thin walls, excellent axial bending strength, and excellent environmental stress crack resistance. 'With the emergence of 572901 and a hollow formed body made of this resin. (3) Summary of the invention The problem to be solved by the present invention is to solve the above-mentioned problems of the prior art, and to provide a hollow with high density, excellent axial bending strength, excellent bottle ESCR, and difficult to cause environmental stress cracking. A polyethylene resin for a molded body and a hollow molded body formed from the resin solve the problem. The polyethylene resin for a hollow molded body according to the present invention is characterized by its melt flow rate (MFR; JIS K7210, 190. (:, 2.16 kg load, unit is g / 10 minutes) is 0.1 ~ 2.0, density (JIS K6922-2, measurement sample is MFR strands, annealing in boiling water for 30 minutes, unit is kg / m3) In the range of 95 7 to 967, and Mz (Z average molecular weight) satisfies the formula Mz ^ -4x1 05 logMFR + 1.2X106 〇 The polyethylene resin is preferably a polyethylene, and its melt measured under a load of 21.6 kg The flow rate (MFR2 1.6) 値 divided by the melt flow rate (MFR2.16) measured under a load of 2.16 kg ([MFR21.6) / (MFR2.16)] is preferably 200 or less. Furthermore, the present invention The polyethylene hollow formed body contains at least The layer is made of the polyethylene-based resin for a hollow molded body, and is suitable for storing lotions, bleaches, softeners, etc. Embodiments of the Invention The polyethylene-based resin for a hollow molded body according to the present invention has been described in detail above. And the hollow formed body formed by using this resin. -8- 572901 Raw._Polyethylene resin for hollow formed body The melt flow rate of polyethylene resin for hollow formed body according to the present invention (MFR; JIS K7210, 190 ° C, 2.16 kg load in grams / 10 minutes) in the range of 0.1 to 2.0 g / 10 minutes, preferably in the range of 0.1 to 1.0 g / 10 minutes, more preferably 0.1 to 0.7 g In the range of / 10 minutes. If the melt flow rate is in this range, the formability is better. Also, its density (JIS K6922-2, the measurement sample is MFR strands, and annealing in boiling water for 30 minutes, the unit is 1 ^ / 1113) is in the range of 95 7 to 967 1 ^ / 1113, preferably in the range of 95 7 to 963 kg / m3. If the density is in this range, the axial bending strength is better. 'The polyethylene resin for a hollow molded body according to the present invention is characterized by using a GP The Mz (average molecular weight of Z) measured by C (gel permeation chromatography) satisfies the formula Mz ^ -4xl05 logMFR + 1.2x106. When Mz satisfies this range, it means that in terms of the ratio of average molecular weight, there is a high molecular weight component. Existence. If M z is within this range, the bottle e SCR is preferred. M z (average molecular weight of Z) is measured as follows by GPC-150 manufactured by Otas Corporation. Separation column is 2 TSK GMH 6ΗΤ and 2 TSK GMH6HTL made by Tosoh (stock), total 4 pieces, column temperature is 14 (TC, mobile phase uses o-dichlorobenzene (made by Wako Pure Chemical Industries, Ltd.)) As the antioxidant, 0.025% by weight of BHT (3,5-di-tert-butylhydroxytoluene) (manufactured by Takeda Pharmaceutical Industry Co., Ltd.) was used, and the sample was moved at 1.0 ml per minute, and the sample concentration was 〇; The injection volume of the sample is 500 microliters, and the detector is a micro-differential refractometer. Standard polystyrene manufactured by Tosoh Corporation is used to calibrate the column by the standard method and converted to polystyrene ^ -9- 572901 The ratio of the melt flow rate (MFR21.6) measured under a load of 21.6 kg to the melt flow rate (MFR2.16) measured under a load of 2.16 kg of the above polyethylene resin is also [(MFR21 .6) / (MFR2.16)]-generally below 200, preferably between 190 and 30, more preferably between 180 and 40, and sufficient impact strength, especially drop strength, can be obtained. Polyethylene used in the present invention The resin is a high-density polyethylene having the above-mentioned relationship between MFR, density, and Mz. Not only an ethylene homopolymer, but also ethylene can be used. Copolymerization of a small amount of α-olefin, for example, with propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl- An ethylene-α-olefin copolymer made of α-olefins such as 1-pentene and 4-methyl-1-pentene. These α-olefins can be used alone or in combination of two or less. High-density polyethylene can be polymerized by Ziegler catalyst or metallocene catalyst, etc., by low pressure method or medium pressure method such as Phillips method, polymerizing ethylene or α-olefins with 3 to 20 carbon atoms In the present invention, the copolymerization of ethylene and α-olefin is performed in a gas phase or a slurry-like liquid phase or in a solution. In terms of slurry polymerization, an inert hydrocarbon can be used as a solvent, and the olefin It can also be used as a solvent. When slurry polymerization or solution polymerization is used, the polymerization temperature is usually in the range of -50 to 250 ° C, and when gas phase polymerization is used, the polymerization temperature is usually in the range of 0 to 120 °. In the range of C, it is preferably in the range of 20 to 100 ° C. The polymerization pressure is usually under the pressure of normal pressure to 100 atm. The polymerization reaction system can be performed in a batch or semi-continuous manner. It can be carried out continuously or continuously. In addition, the polymerization reaction can also be divided into two or more stages with different reaction conditions, including preliminary polymerization, single stage, and multi-stage can accelerate the polymerization reaction. -10- 572901 Because Mz is obtained by the average molecular weight calculation method that has a large influence on high molecular weight components. Although the presence of high molecular weight but high fluidity can reach the target range of MFR and Mz. Specifically, if the molecular weight distribution is wide, The existence of high molecular weight components may achieve the range relationship between MFR and Mz in the scope of the patent application. In addition, in order to produce polyethylene with a wide molecular weight distribution and high molecular weight components, multi-stage polymerization can be performed (a method of continuously producing polyethylenes having different molecular weights and densities by continuously using reactors such as two-stage polymerization and three-stage polymerization) or melt blending. Multi-stage polymerization or melt blending can be used to blend Mz and MFR within the target range by blending more than two types of low molecular weight polyethylene and high molecular weight polyethylene. In addition, the above-mentioned physical properties can also be achieved by blending polyethylene produced by the high-pressure method with the polyethylene resin of the present invention. In this case, a high-pressure process polyethylene having a density of about 9 10 to 9 3 5 kg / m3 is used. The weight ratio of the polyethylene resin to the high-pressure polyethylene that can be used in the present invention is usually 100 to 65/0 to 35, preferably 100 to 80/0 to 20. From the viewpoint of moldability, a high-pressure polyethylene method within this range is preferred. Further, various additives can be blended in the polyethylene-based resin or the polyethylene-based resin composition within a range that does not impair the physical properties of the hollow molded body. Specific examples of the additives are fillers, weather-resistant stabilizers, heat-resistant stabilizers, antistatic agents, anti-slip agents, anti-fog agents, slip agents, pigments, dyes, core agents, plasticizers, flame retardants, hydrochloric acid absorbents, etc. . Worm Hollow Molded Body The hollow molding system according to the present invention is formed of the above-mentioned polyethylene-based resin or polyethylene-based resin composition. The hollow formed body according to the present invention may be formed from a single layer in the form of a single-layer container, and may also be formed in the form of a multilayer container from two or more layers. For example, when a multilayer container is formed of two layers, one layer is formed of the polyethylene-based resin preferably used in the present invention, and the other layer is formed of a resin different from the polyethylene-based resin, or the above-mentioned The polyethylene-based resin preferably used in the invention is formed, and one layer may be formed of a polyethylene-based resin having physical properties different from those of the polyethylene-based resin used. The different resins mentioned above are, for example, polyamide (nylon 6, nylon 66, nylon 12, copolymerized nylon, etc.), ethylene · vinyl alcohol copolymer, polyester (polyethylene terephthalate, etc.), modified polyolefin, etc. . The hollow formed body according to the present invention can be produced by a conventional hollow forming (blow molding) method. There are various methods of blow molding, and they are roughly classified into extrusion blow molding, two-stage blow molding, and injection molding. In the present invention, an extrusion blow molding method is preferably used. The hollow molding system prepared above is suitable for use in bleach containers, lotion containers, bleach containers, etc., for example, it is suitable for domestic use in cosmetics, softening agents, shampoos, moisturizers, treatment agents, etc. • Surfactant container or bleach container for business use. ADVANTAGE OF THE INVENTION The first polyethylene-based resin for hollow formed bodies according to the present invention is characterized by its melt flow rate (MFR; JIS K72 1 0, 1 90 ° C, 2.16 kg load, unit is g / 10 minutes ) System 0 · 1 to 2.0, density (JIS K6922-2, the measurement sample is MFR-based strands, and annealed in boiling water for 30 minutes, the unit is kg / m3) is in the range of 957 to 967, and GPC (coagulation Gel permeation chromatography) -12- 572901 The Mz (average molecular weight of Z) measured satisfies the formula Mzg-4xl05 logMFR + 1 · 2x1 〇6, and it has sufficient axial bending strength and environmental resistance even for thin-walled containers. Stress cracking. The melt flow rate (MFR21.6) measured at 190 ° C under a load of 21.6 kg of a polyethylene-based resin for a hollow formed body according to the present invention and the melt velocity measured at a load of 2.16 kg When the ratio ([MFR21.6) / (MFR2.16)] of the body flow velocity (MFR2.16) 値 is less than 200, the drop strength is also excellent. The polyethylene resin for hollow formed bodies and the hollow formed system of the present invention are suitable for lotions, shampoos, moisturizers, bleaching agents, softening finishing agents, cosmetics, waxes, edible oils, salad dressings, mustard sauces, etc. Container, fuel tank, industrial medicine tank, cylinder tank, water tank, etc. (IV) Sinus application mode The present invention will be described below by way of examples, but the present invention is not limited to these examples at all. The melt flow rate (MFR), density, Mz (Z average molecular weight), tensile impact strength, and environmental stress crack resistance F50 were measured based on the following methods. MFR: JIS K7 210, 190 ° C, 2.16 kg load density: JIS 6922-2, the measurement sample is MFR strands, and annealed in boiling water for 30 minutes. Μζ: Use GPC-150 manufactured by Wardex, as follows Determination. Separation column is 2 TSK GMH 6ΗΤ and 2 TSK GMH6HTL made by Tosoh (shares). The total number is 4. The column temperature is i40 ° C. The mobile phase uses o-13-572901 dichlorobenzene (Wako Pure Chemical Industries, Ltd.) (Manufactured by Stock Co., Ltd.), the antioxidant used was 0.025% by weight of BHT (3,5-di-tert-butylhydroxytoluene) (manufactured by Takeda Pharmaceutical Industry Co., Ltd.), and moved at 1.0 ml per minute. The concentration is 0. 1% by weight, the sample injection volume is 500 microliters, and the detector is a micro differential refractometer. The column was calibrated using standard polystyrene manufactured by Tosoh Corporation and converted to polystyrene. Tensile impact strength: It was measured based on JIS K7160 using a JIS K7160 type 4 test piece. Environmental stress cracking resistance F50 値: Based on ASTM D1693 B method, with Antalox Co.63 0 as the surfactant, and measured with 10% aqueous solution. Example: Using a catalyst in the coexistence of ethylene and 1-butene, the MFR under a 2.16 kg load is 0.8 g / 10 minutes, and the MFR under a 21.6 kg load is 80 g / 10 minutes. And the polyethylene with a density of 9 5 9 kg / m3, similarly produced by multi-stage polymerization, has an MFR of 0.04 g / 10 min under a load of 2.16 kg, an MFR of 7.4 g / 10 min under a load of 21.6 kg and a density It is 959 kg / m3 of polyethylene. The two polyethylenes described above were melt blended at a ratio of 80:20. The MFR of the melt-blended polyethylene under 2.16 kg load was 0.41 g / 10 minutes, the MFR under 21.6 kg load was 50 g / 10 minutes, the density was 959 kg / m3, and the Mζ determined by GPC was 16.7 × 105 . The tensile impact strength was 130 kJ / m2, and the environmental stress crack resistance F50 値 was 300 hours. The results are shown in Table 1. < Forming conditions of single-layer hollow formed article > -14- 572901 Next, using an extrusion blow molding machine (manufactured by Japan Steel Corporation, model: JEB-15), the forming temperature of polyethylene was 20 (TC Resin extrusion volume: 50 kg / hour, mold temperature: 20 ° C, the polyethylene is blow molded to obtain cylindrical bottles (single layer) with a content of 780 ml, weights of 25 g and 35 g Hollow formed body), and a bottle with a handle of 2.5 liters and a weight of 130 g (single-layer hollow formed body). ≪ Repeated drop test method of single-layer hollow formed body > The bottle was subjected to a repeated drop test. The results are shown in Table 1. A single-layer bottle with a content of 780 ml and a weight of 25 g was filled with water, and the bottle was erected at a certain height in an environment of 0 ° C. Drop, repeat 10 times at most. Through the drop test, measure the number of repeated drops when water leaks from the cracks to the outside. Repeat this test 10 times to determine the average number of drops when the bottle forms a crack. The bed used to drop the bottle uses 2 Inch thick iron plate Condensate bed. ≪ Test method of axial bending strength of single-layer hollow formed body > Using an Intron universal testing machine at a test temperature of 15 mm per minute at a test temperature of 30 ° C and a content of 780 ml and a weight of 35 g The single-layer bottle was compressed, and the maximum strength obtained was taken as the axial bending strength. The results are shown in Table 丨. <Single-layer hollow formed body bottle ESCR test method> The content is 780 ml and the weight is 35 grams The cylindrical bottle was filled with 78 cc of the following content liquid. In a bottle with a handle of 2.5 litres and a weight of 130 grams, 250cc of the following content liquid was filled, and then it was sealed and stored at 65 Art. Observe the bottle. Time when cracks occurred. The measured η number of the bottles was 10 each. -15-572901 After the test was started, the time when cracks occurred in the first bottle was recorded. The results δ are shown in Table 1. Chlorine Bleaching agent: Kao (stock) from Jin Haida oxygen-based bleaching agent: Lion King (manufacturing) Temanasi bleach softener: Kao (stock) Haimiku shampoo: Shiseido (stock) Bamalud Shampoo < 3 types of five-layer hollow shaped body forming method and bottle ESCR test Method > The polyethylene was blow-molded using an extrusion blow-molding machine (manufactured by Japan Steel Co., Ltd., model: 〖EB-105PC). The molding temperature was 20 (TC, resin extrusion amount: 10 kg). / Hour, mold temperature: 20 ° C, and a cylinder bottle with an inner volume of 500 ml and a weight of 25 g was obtained. The thickness composition ratio of each layer was polyethylene: adhesive resin: ethylene • vinyl alcohol copolymer: adhesive resin: polyethylene = 41 ·· 3: 2: 3: 41. Adidas NB508 made by Mitsui Chemicals Co., Ltd. was used as the adhesive resin, and Aibaru F101B made by Kuraray Co., Ltd. was used as the ethylene / vinyl alcohol copolymer. The obtained bottle was filled with 50 cc of a chlorine-based bleach (made by Kao (Jin Haida) Co., Ltd.), and then sealed, stored at 65 ° C, and the time when the bottle was cracked was observed. The η numbers of the bottles measured were 10 each. After the test was started, the time when the first bottle cracked was recorded. The results are shown in Table 1. < Two types of two-layer hollow formed body forming method and bottle ESCR test method > In addition, an extrusion blow molding machine (produced by Braco, model: Braco-3B-50-4 0) was used, This polyethylene was blow-molded, forming temperature: 20 ° C, resin extrusion amount: 8 kg / hour 'mold temperature: 20 ° C, and a cylindrical bottle with a content of 1000 ml and a weight of 40 g was obtained. The outer layer is polyethylene, and the inner layer is -16- 572901 single-layer hollow molded product crushed product. The thickness composition ratio of each layer is the outer layer: inner layer = 80:20. The obtained bottle was filled with 100CC chlorine bleach (from Kao (Jin) Co., Ltd.), and then sealed, stored at 65 ° C, and the time when the bottle cracked was observed. The measured η numbers of the bottles were each 10 pieces. The time when the first bottle was cracked was recorded after the test was started. The results are shown in Table 1. Sinus Example 2 A polymer having a MFR of 2.16 kg was -29 g / 10 minutes, a MFR2 of 1.6 kg was 39 g / 10 minutes, a density was 9 59 kg / m3, a Mζ was 16.0 × 105, and a tensile impact strength was 170 kJ / m2. Except that ethylene was used instead of the polyethylene of Example 1, the same procedure as in Example 1 was performed. The results are shown in Table 1. Example 3 Instead of melt blending, the MFR 2.16 kg adjusted to 0.38 g / 10 min, the MFR2 1.6 kg to 57 g / 10 min, and the density adjusted by the low-quantity and high-molecular-weight components continuously produced by multi-stage polymerization were used. Instead of the polyethylene of Example 1, a polyethylene of 9 5 9 kg / m3, Mζ of 18.7 × 105, and tensile impact strength of 110 kJ / m2 was examined in the same manner as in Example 1. The results are shown in Table 1. Example 4 MFR 2.16 kg was 0.16 g / 10 min, MFR 21.6 kg was 25 g / 10 min, density was 95 9 kg / m3, Mζ was 20 · χχ 105, and tensile impact strength was 22 k. Except that the polyethylene of J / m2 was used in place of the polyethylene of Example 1, it was examined in the same manner as in Example 1. The results are shown in Table 1. Example 5 -17-572901 Use MFR 2.16 kg 0.49 g / 10 min, MFR 21.6 kg 56 g / 10 min, density 960 kg / m3, Mz 15.4x105, tensile impact strength 120 kJ / m2 The same procedure as in Example 1 was performed except that the polyethylene was replaced by the polyethylene of Example i. The results are shown in Table 1. Example 6 A polyethylene having MFR 2.16 kg of 0.29 g / 10 minutes, MFR 21.6 kg of 30 g / 10 minutes, a density of 961 kg / m3, a Mz of 16.0x105, and a tensile impact strength of 1 80 kJ / m2 was used. Instead of the embodiment! Except for polyethylene, the same procedures as in Example 1 were performed. The results are shown in Table 1. Comparative Example 1 A polymer having MFR 2.16 kg of 0.36 g / 10 minutes, MFR 21.6 kg of 35 g / 10 minutes, a density of 955 kg / m3, a Mz of 12.1 x 105, and a tensile impact strength of 210 kJ / m2 was used. Ethylene instead of example! Except for polyethylene, the same procedures as in Example 1 were performed. The results are shown in Table 1. Comparative Example 2 A polyethylene having MFR 2.16 kg of 0.36 g / 10 min, MFR 21.6 kg of 35 g / 10 min, a density of 95 9 kg / m3, a Mz of 12.5x105, and a tensile impact strength of 200 kJ / m2 was used. Except for the polyethylene of Example i, the same procedure as in Example 1 was performed. The results are shown in Table 1. Comparative Example 3 A MFR of 2.16 kg was 0.40 g / 10 minutes, a VIFR of 21.6 kg was 84 g / 10 minutes, a density was 959 kg / m3, a Mz was 20.1 x 100, and a tensile impact strength was 80 kJ / m2. Except that polyethylene was used instead of the polyethylene of Example 1, it examined similarly to Example 1. 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