200302835 玖、發明說明 (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烯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9 5 7 kg/cm3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E S C R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 200302835 及一種由該樹脂所成的中空成形體之出現。 (三）發明內容 發明所欲解決的問題 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E S C R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 解決問顆的半段 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°C，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/cm3)係 在957〜967的範圍內，而且Mz (Z平均分子量）滿足式Mz ^ -4x1 05 logMFR + 1.2xl06。 上述聚乙烯系樹脂較佳爲一種聚乙烯，其在2 ；1 . 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 2 00 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。 發明的實施形熊 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- 200302835 中空成形體用聚乙烯系p哨 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 5 單位爲克 /1〇 分 鐘）係在〇 · 1〜2 · 0克/1 〇分鐘的範圍內，較佳在〇」〜丨.〇公斤 /1 〇分鐘的範圍內，更佳在〇 . 1〜〇 . 7公斤/ 1 0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kg/cm3)係在957〜967 kg/cm3 的範圍內，較佳在9 5 7〜9 6 3 kg/cm3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^-4x1〇5 logMFR + 1.2X106。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GPCN150 如下來測定。 分離管柱爲2支東曹（股）製TSK GMH 6HT和2支TSK GMH 6HTL，合計4支，管柱溫度爲140°C，移動相使用鄰 二氯苯（和光純藥工業（股）製），抗氧化劑使用0.02 5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5 0 0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- 200302835 又，藉由使上述聚乙烯系樹脂之在2 1 · 6公斤荷重下測定 的熔體流速（MFR2 1.6)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1 90〜30，更佳在1 80〜40，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M F R、密度和 Μζ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、卜己烯、3 -甲基-卜 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3〜2 0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20〜10CTC的範圍內。聚合壓 力通常在常壓至l〇〇atm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- 200302835 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M FR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 1 0〜9 3 5 kg/cm3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丨00〜6 5/0〜35， 較佳1 0 0〜8 0 / 0〜2 0。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。 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 乙細系樹脂組成物所形成。本發明所關於的中空成形體可 -11- 200302835 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 使用的聚乙儲系樹脂來形成’ 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 K7210，190°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M F R計股束，在沸水中退火3 0分鐘，單位爲k g / c m3) 係在9 5 7〜9 6 7的範圍內，而且使用G P C (凝膠滲透層析術） 200302835 所測定的Mz (Z平均分子量）滿足式Mz-_4xl05 logMFR + 1·2χ1 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）實施方式 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。 乂？&:】13匕7 210，190°(：52.16公斤荷重 岔度：J I S K 6 9 2 2 - 2，測定樣品爲M F R計股束，在沸水 中退火3 0分鐘 Μ ζ :使用沃答斯公司製g P C -1 5 0，如下測定。 分離管柱爲2支東曹（股）製TSK GMH 6ΗΤ和2支TSK GMH 6HTL，合計4支，管柱溫度爲14〇它，移動相使用鄰 200302835 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0.1重量％，試料注入 量爲5 0 0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〇6 3 0當作界面活性劑，以10%水溶液來測 疋。 實施例1 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959k g/cm3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0.04 克/10分鐘、21.6公斤荷重下的MFR爲7.4克/10分鐘且密 度爲9 5 9k g/cm3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 . 1 6公斤荷重下的 MFR爲〇·41克/10分鐘，21.6公斤荷重下的MFR爲50克/10 分鐘，密度爲9 5 9kg/cm3，GPC所測定的Mz爲16.7X105。 又，拉伸衝撃強度爲130kJ/m2，耐環境應力龜裂F50値 爲3 0 〇小時。其結果記載於表1中。 <單層中空成形體之成形條件> -14- 200302835 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：2〇(rc、樹脂擠出量：5〇 公斤/小時、模具溫度·· 2 0 °C的成形條件下，將該聚乙烯吹 塑成形’而得到內谷量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13〇克的 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0°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1 5 m m，在3 0 °c試驗 溫度對內容量7 8 0毫升、重量3 5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1中。 <單層中空成形體的瓶E S C R試驗法〉 、 於內容量780毫升、重量35克的圓筒瓶中塡充78cc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25 Occ下述內容液，然後密閉，於651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， -15- 200302835 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。 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：JEB_ 105PC)，將該聚乙烯吹塑成形，成形溫度：20(TC，樹脂擠 出量：1 〇公斤/小時，模具溫度：2 0 °C ’而得到內容量5 0 0 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=4 1 : 3 : 2 : 3 : 4 1。而且，黏著樹脂係使 用三井化學（股）製的阿德馬N B 5 0 8，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 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。 <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-3 Β- 5 0-4 0)，將該聚乙烯吹塑成形，成形溫度·· 200 °C，樹 脂擠出量：8公斤/小時，模具溫度：20 °C，而得到內容量 1000毫升、重量40克的圓筒瓶。外層爲聚乙烯，內層爲 200302835 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lOOcc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。 實施例2 使用MFR2.16公斤爲0.29克/10分鐘、MFR21 .6公斤爲 39克/10分鐘、密度爲959kg/cm3、Mz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公斤爲〇·38克/10分 鐘、MFR2 1.6公斤爲57克/10分鐘、密度爲9 5 9kg/cm3、Mz 爲1 8 · 7 x 1 0 5、拉伸衝擊強度爲1 1 0 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959kg/cm3、Mz爲20·〇χΐ〇5、拉伸 衝擊強度爲220kJ/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。 實施例5 > 17- 200302835 使用MFR2.16公斤爲0.49克/10分鐘、MFR2 1.6公斤爲 56克/10分鐘、密度爲960kg/cm3、Mz爲15.4X105、拉伸 衝擊強度爲UOkj/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 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/cm3、Mz爲16.0X105、拉伸 衝擊強度爲180kJ/m2的聚乙烯來代替實施例}的聚乙稀， 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/1〇分鐘、MFR21.6公斤爲 35克/10分鐘、密度爲95 5kg/cm3、Mz爲12·1χ1〇5、拉伸 衝擊強度爲2 1 OkJ/m2的聚乙烯來代替實施例1的聚乙燃， 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/1〇分鐘、MFR21.6公斤爲 35克/10分鐘、密度爲959kg/cm3、Mz爲Ι2·5χ105、拉伸 衝擊強度爲2〇〇kJ/m2的聚乙烯來代替實施例1的聚乙稀， 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/1〇分鐘、MFR21.6公斤爲 84克/10分鐘、密度爲9 5 9kg/cm3、mz爲20·1χ1〇5、拉伸 衝擊強度爲8 0 k J / lrr的聚乙燦來代替實施例1的聚乙燒， 以外與實施例1同樣地進行檢討。其結果記載於表1中。 -18- 200302835 I漱 比較例3 寸 〇 ^_ 20.1X105 |13·6χ105 1 210 _ 2.8 500 500以上 500以上 500以上 500以上 500以上 500以上 500以上 比較例2 0.36 959 12.5X105 |13.8xl05 to m r- |310 200 6.2 Ο to 110 〇 (Ν 320 400 比較例1 0.36 |955 12.1x10s |l3.8xl05 yr) m 卜 ON m_ 210 卜 300 ; 500以上 500以上 500以上 500以上 500以上 500以上 1__ 500以上 實施例6 ^_ |961 16.0x10s |14.2χ105 ο cn 103 _! 180 σ\ 卜 230 500以上 500以上 500以上 500以上 500以上 500以上 500以上 實施例5 0.49 |960 | 15.4x10s |l3.2xl05 1 寸 |320 | 120 On 250 500以上 500以上 500以上 500以上 500以上 500以上 500以上 實施例4 〇 ^_ 20.0X105 |15.2χ105 ι <N 156 _ 220 〇〇 500 500以上 500以上 500以上 500以上 500以上 500以上 500以上 實施例3 0.38 |959 18.7x10s |ΐ3.7χ105 ι r- 150 o m o (N 350 500以上 500以上 500以上 500以上 500以上 500以上 500以上 實施例2 0.29 |959 16.0X105 |ΐ4·2χ105 ι 〇\ m 134 o 1 70 卜 400 500以上 500以上 500以上 500以上 500以上 500以上 500以上 實施例1 寸 〇 |959 16.7x10s 13.5χΙ05 122 I310_ 130 oo 300 500以上 500以上 500以上 1500以上 500以上 500以上 500以上 |單位 克/10分鐘 kg/cm3 1 1 克no分鐘 1 z KJ/m2 小時 小時 小時 小時 小時 小時 小時 七 小時 MFR2.16公斤荷重 密度 Mz -4x1 Ο5 log(MFR) + 1 .2x1 Ο6 MFR2 1 .6公斤荷重 MFR21.6荷重/MFR2.〗6荷重比 軸向彎曲強度 拉伸衝擊強度 落下強度 耐環境應力龜裂（F50) /-^N ffi ^ κ |» 1拗 ，钷 /^s ^ K ω Mi 踣祕 1¾ £ίφ ，過 0^ 一 ^ S 错献 Zm ，诞 單層中空成形體的瓶ESCR (圓筒瓶：內容液洗髮精） PU Μ髮 5姊 <η. m is匿 鍥匿 创恢 A- IS ,蹩 丨丨掷 (N w —61丨200302835 发明 Description of the invention (The description of the invention should state: the technical field, prior art, contents, embodiments, and drawings of the invention briefly) (1) Technical field to which the invention belongs The present invention relates to a polyethylene resin for hollow formed bodies And a hollow formed body made of the resin. More specifically, the present invention relates to a polyethylene resin for a hollow formed body, which can produce a hollow formed body that has excellent axial bending strength, environmental load resistance (bottle ESCR), and impact resistance, and has excellent appearance. , And about and formed from this resin. (2) Prior art Conventionally, in the hollow formed body, from the viewpoint of resource conservation and waste reduction, it is necessary to reduce the amount of resin used. However, when it is 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 axial bending strength, it is effective to use a high-density polyethylene resin based on high density. However, in the case of using a polyethylene material having a density of 9 5 7 kg / cm3 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 , And easy to crack, it is difficult to be practical. Therefore, the appearance of a polyethylene-based resin for a hollow molded body is expected, which is composed of a high-density polyethylene-based resin that can produce a hollow molded body with high density, thin walls, excellent axial bending strength, and excellent environmental stress crack resistance. With the appearance of 200302835 and a hollow formed body made of this resin. (3) Summary of the Invention Problems to be Solved by the Invention The object of the present invention is to solve the problems of the prior art described above, and provide a hollow molding with high density, excellent axial bending strength, excellent bottle ESCR, and environmental stress cracking that is difficult to occur. Polyethylene resin for body and half of the hollow shaped body made of the resin to solve the problem The polyethylene resin for hollow shaped body of the present invention is characterized by its melt flow rate (MFR; JIS K7210, 190 ° C, 2.16 kg load, unit is g / 10 min. Is 0.1 ~ 2.0, density (JIS K6922-2, measurement sample is MFR strand, annealing in boiling water for 30 minutes, unit is kg / cm3) is 957 In the range of ~ 967, and Mz (Z average molecular weight) satisfies the formula Mz ^-4x1 05 logMFR + 1.2xl06. The above-mentioned polyethylene-based resin is preferably a polyethylene having a melt flow rate (MFR2 1.6) measured under a load of 1.6 kg and 1.6 kg divided by a melt flow rate (MFR 2.16) measured under a load of 2.16 kg The obtained fluorene [(MFR21.6) / (MFR2.16)] is preferably 2000 or less. The polyethylene hollow molded body according to the present invention contains at least one layer made of the above-mentioned polyethylene resin for a hollow molded body, and is suitable for storing lotions, bleaches, softeners, and the like. Embodiment of the invention The above-mentioned concrete description is made of a polyethylene resin for a hollow formed body according to the present invention, and a hollow formed body formed using the resin. -8- 200302835 Polyethylene p-whistle for hollow formed body The melt flow rate of polyethylene-based resin for hollow formed body (MFR; JIS K7210, 190 ° C, 2.16 kg load 5) The unit is g / 1 Minutes) is in the range of 0.1 to 2.0 grams per 10 minutes, preferably in the range of 0.1 to 0.1 kg per minute, and more preferably 0.1 to 0.7 kg per minute. Within 10 minutes. When the melt flow rate is within this range, the formability is better. The density (JIS K6922-2, the measurement sample is MFR-based strands, and annealed in boiling water for 30 minutes, the unit is kg / cm3) is in the range of 957 to 967 kg / cm3, preferably 9 5 7 Within the range of ~ 9 6 3 kg / cm3. If the density is within this range, the axial bending strength is better. Furthermore, the polyethylene resin for hollow formed bodies according to the present invention is characterized in that Mz (Z average molecular weight) measured by GPC (gel permeation chromatography) satisfies the formula Mz ^ -4x105 logMFR + 1.2X106 . When Mz satisfies this range, it means that a high molecular weight component exists in the ratio of average molecular weight. If M z is within this range, the bottle E S C R is preferred. Mζ (average molecular weight of Z) was measured as follows by using GPCN150 manufactured by Otas Corporation. Separation column is 2 TSK GMH 6HT and 2 TSK GMH 6HTL made by Tosoh (stock), total 4 pieces, column temperature is 140 ° C, o-dichlorobenzene (made by Wako Pure Chemical Industries, Ltd.) is used as mobile phase. ), 0.025% by weight of BHT (3,5-di-tert-butylhydroxytoluene) (manufactured by Takeda Pharmaceutical Industry Co., Ltd.) was used as an antioxidant, and was moved at 1.0 ml per minute with a sample concentration of 0.1 wt. %, 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. -9- 200302835 The ratio of the melt flow rate (MFR2 1.6) measured under the load of 2 1 · 6 kg to the melt flow rate (MFR2.16) measured under the load of 2.16 kg値 [(MFR21.6) / (MFR2.16)]-generally below 200, preferably from 1 90 to 30, more preferably from 1 80 to 40, and can obtain sufficient impact strength, especially drop strength. The polyethylene-based resin used in the present invention is a high-density polyethylene having the above-mentioned relationship between MFR, density, and Mζ. Not only an ethylene homopolymer, but also a copolymerization of ethylene with a small amount of α-olefin, for example, with 〇. Mole% or less of propylene, 1-butene, 1-pentene, 3-methyl-1-butene, dihexene, 3-methyl-pentene, 4-methyl-1-pentene, etc. Α-olefin, and an ethylene · α-olefin copolymer. These α-olefins may be used alone or in combination of two or less. The high-density polyethylene based on the above physical properties can be polymerized by ethylene or ethylene with a carbon number of 3 to 2 by a low pressure method or a medium pressure method such as a Phillips method using a Ziegler catalyst or a metallocene catalyst. The α-olefin is adjusted. In the present invention, the copolymerization of ethylene and an? -Olefin is carried out in a gas phase or a slurry-like liquid phase or in a solution. For slurry polymerization, inert hydrocarbons can be used as solvents, and olefins can be used as solvents. When carrying out a slurry polymerization method or a solution polymerization, the polymerization temperature is usually in the range of -50 to 250 ° C. In the gas phase polymerization method, the polymerization temperature is usually in the range of 0 to 120 ° C, which is preferable. In the range of 20 ~ 10CTC. The polymerization pressure is usually under a pressure of normal pressure to 100 atm. The polymerization reaction system can be carried out by any of a batch method, a semi-continuous method, and a continuous method. In addition, the polymerization reaction may be divided into two or more stages with different reaction conditions, and the preliminary polymerization, single stage, and multiple stages can be used to accelerate the polymerization reaction. -10- 200302835 Mz is obtained by the calculation method of average molecular weight with high influence of high molecular weight components. Although high molecular weight is present, the fluidity is high, and the target range of MFR and Mz can be achieved. Specifically, if the molecular weight distribution is wide, it is possible to achieve a range relationship between MFR and Mz in the scope of the patent application due to the presence of high molecular weight components. In addition, in order to produce polyethylene having a wide molecular weight distribution and high molecular weight components, multi-stage polymerization (a method of continuously producing a polyethylene having different molecular weights and densities by continuously using a reactor such as two-stage polymerization and three-stage polymerization) or melt blending can be performed. Multi-stage polymerization and melt blending can be used to blend Mz and M FR within the target range by blending more than two types of low molecular weight polyethylene and high molecular weight polyethylene '. The polyethylene resin produced by the high-pressure method can be blended with the polyethylene resin of the present invention to achieve the above-mentioned physical properties. In this case, a high-pressure polyethylene having a density of about 9 10 to 9 3 5 kg / cm3 is used. The weight ratio of the polyethylene resin of the present invention to the high-pressure method polyethylene that can be used is usually 00 to 6 5/0 to 35, preferably 10 0 to 8 0/0 to 2 0. From the viewpoint of moldability, a high-pressure polyethylene method within this range is preferred. Further, various additives may 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, nuclear agents, plasticizers, flame retardants, hydrochloric acid absorbents, etc. . Hollow formed body The hollow formed 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 Polyethylene storage-based resins that are preferably used in the invention to form a layer may be formed from a polyethylene-based resin having physical properties different from those of the polyethylene-based resin used. The above-mentioned different resins 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 resin for hollow shaped bodies which concerns on this invention is characterized by the melt flow rate (MFR; JIS K7210, 190 ° C, 2.16 kg load, the unit is g / 10 minutes). · 1 ~ 2.0, density (JIS K6922-2, measurement sample is MFR strands, annealed in boiling water for 30 minutes, unit is kg / c m3) is in the range of 9 5 7 to 9 6 7 and used GPC (Gel Permeation Chromatography) 200302835 The Mz (average molecular weight of Z) measured satisfies the formula Mz-_4xl05 logMFR + 1 · 2χ1 〇6, and it has sufficient axial bending strength and environmental resistance even in thin-walled containers. Stress cracking. The melt flow velocity (MFR21.6) of the polyethylene-based resin for a hollow formed body according to the present invention measured at 190 ° C under a load of 21.6 kg and the melt flow rate measured at a load of 2.16 kg When the ratio of the body flow rate (MFR2.16) 値 [(MFR21.6) / (MFR2.16)] is 200 or less, 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 dressing, mustard sauce, etc Container, fuel tank, industrial medicine tank, cylinder tank, water tank, etc. (IV) Embodiments The present invention is described below by examples, but the present invention is not limited to these examples at all. The melt flow rate (MFR), density and Mz (Z average molecular weight), tensile impact strength, and environmental stress crack resistance F50 were measured based on the following methods. Huh? &:] 13 dagger 210, 190 ° (: 52.16 kg load bifurcation: JISK 6 9 2 2-2, the measurement sample is MFR strands, and annealed in boiling water for 30 minutes Μ ζ: using Wadasi company Make g PC -1 50, and measure it as follows. The separation column is 2 TSK GMH 6ΗΤ and 2 TSK GMH 6HTL made by Tosoh (shares), a total of 4 and the column temperature is 14 °. Dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.). As an antioxidant, 0.025% by weight of BHT (3,5-di-tert-butylhydroxytoluene) (manufactured by Takeda Pharmaceutical Industry Co., Ltd.) was used at a rate of 1 · per minute. 〇mL moves, the sample concentration is 0.1% by weight, the sample injection volume is 500 microliters, and the detector is a differential refractometer. Standard polystyrene made by Tosoh Corporation is used to calibrate the column by the standard method. , Converted to polystyrene. Tensile impact strength: JIS K7160-based, measured using JIS K7160 type 4 test specimens. Environmental stress cracking resistance F50 値: Based on ASTM D1693 B method, based on Antara Kerosene Co. 30 was used as a surfactant, and the tritium was measured with a 10% aqueous solution. Example 1 In ethylene and 1-butane In the coexistence of catalysts, polyethylene with a MFR of 0.8 g / 10 min under a load of 2.16 kg, a MFR of 80 g / 10 min under a load of 21.6 kg, and a density of 959 k g / cm3 are produced by multistage polymerization. Polyethylene with a MFR of 0.04 g / 10 min under a load of 2.16 kg, a MFR of 7.4 g / 10 min under a load of 21.6 kg, and a density of 995 kg / cm3 were produced by multi-stage polymerization. Ethylene was melt blended at a ratio of 80:20. The MFR of the melt blended polyethylene at a load of 2.16 kg was 0.41 g / 10 minutes, and the MFR at a load of 21.6 kg was 50 g / 10 minutes. The density was 9 5 9 kg / cm3, and the Mz measured by GPC was 16.7X105. The tensile impact strength was 130 kJ / m2, and the environmental stress crack resistance F50 was 300 hours. The results are shown in Table 1. < Forming conditions of single-layer hollow formed article -14-200302835 Next, using an extrusion blow molding machine (manufactured by Nippon Steel & Co., Ltd., model: JEB-15), the forming temperature of polyethylene was: 20 (rc Resin extrusion: 50 kg / h, blow molding of the polyethylene under molding conditions at a mold temperature of 20 ° C Shape 'to obtain cylindrical bottles with a inner grain volume of 780 ml, weights of 25 g and 35 g (single-layer hollow formed bodies), and bottles with handles of 2.5 liters and a weight of 130 g (single-layer hollow forming) body). < Repeated drop test method of single-layer hollow formed article > Repeated drop test was performed on the bottle obtained as described above according to the following method. 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, the bottle was erected and dropped at a certain height in an environment of 0 ° C, and repeated 10 times at most. With the drop test, the number of repeated drops when water leaks from the crack to the outside is measured. This test was repeated 10 times to determine the average number of drops when the bottle formed a crack. The bed on which the bottle fell was placed horizontally on a concrete bed using a 2-inch thick iron plate. < Test method of axial bending strength of single-layer hollow formed article > Using an Intron universal testing machine, at a test temperature of 15 mm per minute, at a test temperature of 30 ° C, the content was 780 ml and the weight was 35 g When the single-layer bottle is compressed, the maximum strength obtained is taken as the axial bending strength. The results are shown in Table 1. < ESCR test method for single-layer hollow formed bottle> A cylinder bottle with a content of 780 ml and a weight of 35 g is filled with 78 cc of the following content liquid, and a bottle with a handle of 2.5 liter and a weight of 130 g is filled. Fill with 25 Occ of the following content, then seal it, store it in 651, and observe the time when the bottle cracks. The η numbers of the bottles measured were 10 each. -15-200302835 After the test was started, the time when the first bottle cracked was recorded. The results are shown in Table 1. Chlorine-based bleach: Kao (share) from Jin Haida oxygen-based bleach: Lion King (manufactured) Temanasi bleach softener: Kao (share) Haimiku shampoo: Shiseido (share) Spartam Rudd shampoo < 3 types of five-layer hollow formed body forming method and bottle ESCR test method > In addition, an extrusion blow molding machine (manufactured by Japan Steel Co., Ltd., model: JEB_ 105PC) This polyethylene was blow-molded, forming temperature: 20 ° C, resin extrusion amount: 10 kg / hour, mold temperature: 20 ° C 'to obtain a cylindrical bottle with a content of 50 ml and a weight of 25 g The thickness composition ratio of each layer is polyethylene: adhesive resin: ethylene • vinyl alcohol copolymer: adhesive resin: polyethylene = 4 1: 3: 2: 3: 4 1. In addition, Mitsui Chemicals Co., Ltd. is used as the adhesive resin system. Adema NB 508 manufactured by Edelweiss, and Ebalu F101B made by Kuraray Co., Ltd. are filled with 50cc of chlorine-based bleach (from Kao Co., Ltd.) Jinhaida), then sealed, stored at 65 ° C, observe the time when the bottle cracks. The number of η of the bottles was 10 each. After the test was started, the time when cracks occurred in the first bottle was recorded. The results are shown in Table 1. < Two types of two-layer hollow formed body forming method and bottle ESCR test method & gt The polyethylene was blow-molded using an extrusion blow-molding machine (produced by Braco, model: Braco-3 Β-5 0-4 0), and the molding temperature was 200 ° C. Resin extrusion amount: 8 kg / hour, mold temperature: 20 ° C, and a cylinder bottle with a content of 1000 ml and a weight of 40 g is obtained. The outer layer is polyethylene and the inner layer is 200302835 single-layer hollow molded product crushed product. The thickness composition ratio of each layer is the outer layer: the inner layer = 80: 20. The obtained bottle was filled with 100 cc of a chlorine-based bleach (Jin Haida from Kao Co., Ltd.), then sealed, stored at 65 ° C, and observed The time when the bottle cracked. The measured η number of the bottles was 10 each. After the test was started, the time when the first bottle cracked was recorded. The results are shown in Table 1. Example 2 Using MFR 2.16 0.29 g / 10 min for kg, 23.9 g / 10 min for MFR21.6 kg, density of 959 kg / cm3, Mz of 16. 0χ105, and a polyethylene having a tensile impact strength of 170 kJ / m2 was used in place of the polyethylene of Example 1 and was examined in the same manner as in Example 1. The results are shown in Table 1. Example 3 was used without melt blending. The MFR 2.16 kg adjusted by continuous production of low molecular weight and high molecular weight components by multi-stage polymerization is 0.38 g / 10 min, MFR 2 1.6 kg is 57 g / 10 min, density 9 9 9 kg / cm3, Mz Except that the polyethylene having a tensile impact strength of 1 8 7 x 105 and a tensile strength of 110 kJ / m2 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 4 MFR 2.16 kg was 0.16 g / 10 min, MFR 21.6 kg was 25 g / 10 min, density was 959 kg / cm3, Mz was 20 · 〇χΐ〇5, and tensile impact strength was 220 kJ / m2. Except that polyethylene was used instead of the polyethylene of Example}, a review was performed in the same manner as in Example 1. The results are shown in Table 1. Example 5 > 17- 200302835 MFR 2.16 kg was 0.49 g / 10 minutes, MFR2 1.6 kg was 56 g / 10 minutes, density was 960 kg / cm3, Mz was 15.4X105, and tensile impact strength was UOkj / m2. Except for using polyethylene instead of the polyethylene of Example 1, the same procedures as in Example 1 were performed. The results are shown in Table 1. Example 6 Polyethylene of MFR 2.16 kg is 0.29 g / 10 minutes, MFR 21.6 kg is 30 g / 10 minutes, density is 961 kg / cm3, Mz is 16.0X105, and tensile impact strength is 180 kJ / m2. Except for polyethene in Example}, the same procedures as in Example 1 were performed. The results are shown in Table 1. Comparative Example 1 MFR 2.16 kg was 0.36 g / 10 minutes, MFR 21.6 kg was 35 g / 10 minutes, density was 95 5 kg / cm3, Mz was 12.1 x 105, and tensile impact strength was 2 Except that polyethylene of 1 OkJ / m2 was used in place of polyethylene in Example 1, it was examined in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 2 MFR 2.16 kg was 0.36 g / 10 minutes, MFR 21.6 kg was 35 g / 10 minutes, density was 959 kg / cm3, Mz was 1.25 x 105, and tensile impact strength was 2000 kJ / m2. Except for using polyethylene instead of polyethylene of Example 1, the same procedures as in Example 1 were performed. The results are shown in Table 1. Comparative Example 3 MFR 2.16 kg was 0.40 g / 10 minutes, MFR 21.6 kg was 84 g / 10 minutes, density was 959 kg / cm3, mz was 20.1x105, and tensile impact strength was 80. Except that polyethylene jcan of k J / lrr was used instead of polyethylene fired of Example 1, it was examined in the same manner as in Example 1. The results are shown in Table 1. -18- 200302835 Comparative example 3 inch 0 ^ _ 20.1X105 | 13 · 6χ105 1 210 _ 2.8 500 500 or more 500 or more 500 or more 500 or more 500 or more 500 or more 500 or more 500 or more Comparative example 2 0.36 959 12.5X105 | 13.8xl05 to m r- | 310 200 6.2 Ο to 110 〇 (N 320 400 Comparative Example 1 0.36 | 955 12.1x10s | l3.8xl05 yr) m BU ON m_ 210 BU 300; 500 or more 500 or more 500 or more 500 or more 500 or more or 500 or more 1__ 500 Example 6 above ^ _ | 961 16.0x10s | 14.2 x 105 ο cn 103 _! 180 σ \ Bu 230 500 or more 500 or more 500 or more 500 or more 500 or more 500 or more or more 500 or more Example 5 0.49 | 960 | 15.4x10s | l3.2xl05 1 inch | 320 | 120 On 250 500 or more 500 or more 500 or more 500 or more 500 or more 500 or more 500 or more Example 4 〇 ^ _ 20.0X105 | 15.2 × 105 ι < N 156 _ 220 〇500 500 or more 500 or more 500 or more 500 Above 500 Above 500 Above 500 Above Example 3 0.38 | 959 18.7x10s | ΐ3.7χ105 ι r- 150 omo (N 350 500 Above 500 Above 500 Above 500 Above 500 Above 500 Above 500 Above 500 Above Example 2 0.29 | 959 16.0X105 | ΐ4 · 2χ105 ι 〇 \ m 134 o 1 70 Bu 400 500 or more 500 or more 500 or more 500 or more 500 or more or 500 or more Example 1 inch 0 | 959 16.7x10s 13.5χΙ05 122 I310_ 130 oo 300 500 or more 500 or more 500 or more 1500 or more 500 or more 500 or more 500 or more units G / 10 minutes kg / cm3 1 1 gram no minutes 1 z KJ / m2 hours hours hours hours hours hours seven hours MFR 2.16 kg load density Mz -4x1 Ο5 log (MFR) + 1.2x1 〇6 MFR2 1.6 kg Load MFR21.6 Load / MFR2. 6 load ratio axial bending strength tensile impact strength drop strength environmental stress crack resistance (F50) /-^ N ffi ^ κ | »1 拗 ， 钷 / ^ s ^ K ω Mi Secret 1¾ £ ίφ, pass 0 ^ a ^ S staggered Zm, single-layer hollow shaped bottle ESCR (cylinder bottle: content liquid shampoo) PU Μ 发 5 姐 < η. 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