200927083 九、發明說明 【發明所屬之技術領域】 本發明係關於醫療容器用多層體及具有由此醫療容器 用多層體所形成的藥液收容部之醫療容器。 【先前技術】 作爲醫療領域所使用的樹脂製之醫療容器，有：安瓶 0 (針藥瓶，ampule)，小藥瓶（vial)、注射容器、由薄 膜形成的輸液袋等。另外，樹脂係使用：聚乙烯或聚丙烯 等之聚烯烴、苯乙烯系彈性體、氯化乙烯樹脂、乙烯一醋 酸乙烯共聚物、環狀聚烯烴等。 此等樹脂中，聚乙烯雖因衛生性高且柔軟，於燃燒處 分時，不會產生有毒氣體等，被廣泛使用於醫療容器，但 是，另一方面，於醫療容器中之與藥液的接液部，如使用 聚乙烯時，藥液中的聚乙烯會吸附脂溶性維他命等之特定 II 的藥劑，得知會有在保存中，該特定藥劑的濃度降低的情 形。 因此，得以抑制特定的藥劑之吸附或吸收所引起的藥 劑的效力降低，且透明性、耐熱性、衛生性等優異，進 而，水蒸氣透過率低等之具有高阻絕性的環狀聚烯烴，作 爲醫療容器的材料正逐漸被廣爲使用。使用環狀聚烯烴的 醫療容器，事先將藥劑塡充於注射器容器的預先塡充注射 器正在普及中。 另外，於專利文獻1記載有：於由熱可塑性飽和降冰 -4- 200927083 片烯系單體所形成的環狀聚烯烴層組合合成樹脂層或阻絕 層等之多層構造醫療容器。 於專利文獻2記載有由具備：表層、柔軟層、阻絕 層、密封層之多層薄膜所形成，於阻絕層使用環狀聚嫌烴 與乙烯-α-烯共聚物，於其他層使用乙烯-α-烯共聚物爲 主成分之醫療容器。 於專利文獻3記載有：於由環狀聚烯烴等之樹脂所形 φ 成的Α層之單面或雙面，層積有由具備特定的融點與維卡 特（Vicat)軟化點之直鏈型低密度聚乙烯所形成的B層 之層積薄膜、及使用此之醫療容器。 進而於專利文獻4記載有：使用於包含特定融點的聚 烯烴系樹脂爲主成分之基材層，層積有包含以特定的玻璃 態轉化溫度的環狀聚烯烴系樹脂爲主成分之密封劑層之層 積薄膜的醫療容器。 [專利文獻1]日本專利第3227709號公報 〇 [專利文獻2]國際專利公開第03/0973 5 5號小冊子 [專利文獻3]日本專利特開2004- 1 67800號公報 [專利文獻4]日本專利特開2005-254508號公報 【發明內容】 [發明所欲解決之課題] 但是，如專利文獻1的段落0027或專利文獻2的段 落0004所記載般，環狀聚烯烴具有接著性不好之缺點。 因此，於製造專利文獻1的多層薄膜時，在環狀聚烯烴層 -5- 200927083 _ 與其他層的層積時，有不得不使用接著劑的情形。可是， 於使用有接著記得多層薄膜中，來自接著劑的成分有釋出 的可能性。因此，如將此種多層薄膜使用於醫療容器，特 別是使用於接近藥液的內側者，從衛生性的觀點而言並不 適合。 於專利文獻2的技術中，爲了改善環狀聚烯烴的接著 性，於環狀聚烯烴混合乙烯-α -烯共聚物，來形成阻絕 ©層。可是，如混合乙烯-α -烯共聚物時，阻絕層的阻絕性 降低，有藥劑被鄰接阻絕層之層吸收之虞。另外，想要改 善阻絕性的降低而將阻絕層變厚時，因而會產生柔軟性降 低的問題。 另外，專利文獻3或4所記載的醫療容器，其耐熱性 不夠充分，無法滿足作爲需要高壓蒸汽來滅菌之醫療容器 的材質。另外，專利文獻3或4所揭示的層積薄膜，也有 耐阻隔性不好的缺點。 ❹ 本發明係有鑑於前述情況所完成者，課題在於提供： 不使用接著劑，由環狀聚烯烴所形成的最內層與其他層可 以良好地接著，耐熱性也優異，在薄膜的情形時，耐阻隔 性也良好的醫療容器用多層體；及由此醫療容器用多層體 所形成，且即使以高壓蒸汽等來滅菌，透明性或剝離強度 等的特性劣化也少的醫療容器。 [解決課題之手段] 本發明之醫療容器用多層體，係使用於醫療容器的形 -6 - 200927083 成之醫療容器用多層體，其特徵爲至少具有__由環狀聚烯 烴所形成的最內層；及鄰接該最內層而形成，且以使用單 一活化部位（single-site)系觸媒所製造的直鏈型低密度 聚乙烯爲主成分之中間層；及含有高密度聚乙烯之最外 層。. 前述環狀聚烯烴，以環狀烯單體的開環聚合物的氫添 加物爲佳。 Q 前述直鏈型低密度聚乙烯的密度，爲0.860 g/cm3以 上且未滿0.940 g/cm3 » 前述高密度聚乙烯的密度，爲 〇.94〇〜0.970 g/cm3 。 前述最外層，爲前述高密度聚乙烯與高壓法低密度聚 乙烯的混合物，或只由前述高密度聚乙烯所形成。 本發明之醫療容器用多層體，爲總厚度60〜1000 ym，且是由：厚度5〜100//m的前述最內層、及前述中 〇 間層、及厚度5〜ΙΟΟμπι的前述最外層之3層所形成。 本發明之醫療容器，係具備有收容藥液之收容部的醫 療容器，其特徵爲：至少前述收容部，係由前述醫療容器 用多層體所形成。 在該情形時，前述醫療容器用多層體，可以是係吹製 成形體。 [發明效果] 如依據本發明，可以提供：即使不使用接著劑’由環 200927083 狀聚烯烴所形成的內層，可與其他層良好地接著，耐熱性 也優異，在爲薄膜之情形時，耐阻隔性也良好的醫療容器 用多層體；及由此醫療容器用多層體所形成，即使以高壓 蒸汽來滅菌，透明性或剝離強度等之特性劣化也少的醫療 容器。 【實施方式】 0 以下，詳細說明本發明。 本發明之醫療容器用多層體，係醫療容器的形成上所 使用，特別是適合使用於醫療容器中收容藥液的收容部的 形成上，至少具有：由環狀聚烯烴所形成的最內層；及鄰 接此最內層而形成，且以使用單一活化部位（single-site )系觸媒所製造的直鏈型低密度聚乙烯爲主成分之中 間層；及含有高密度聚乙烯之最外層。 第1圖係表示本發明之一例的醫療容器用多層體（以 G 下，稱爲多層體）1〇。 此例之多層體1〇，係由：由環狀聚烯烴所形成的最內 層11;及以使用單一活化部位系觸媒所製造的直鏈型低密 度聚乙烯爲主成分之中間層12;及含有高密度聚乙烯之最 外層13依序層積之3層所形成，藉由空冷或水冷之多層 膨脹成形法、多層T模成形法等，而形成爲薄膜者。另 外，在本發明中，彙整薄膜及薄片而統稱爲薄膜。 最內層11繫於從此多層體10來形成醫療容器時’成 爲內側，直接與收容於醫療容器的藥液等接觸之層’由環 -8- 200927083 狀聚嫌烴所形成。 環狀聚烯烴，由於藥劑的吸附或吸收少’藉由將以環 狀聚烯烴所形成的層當成最內層11的多層體10來形成醫 療容器，可以抑制收容的藥液之效力降低。另外，環狀聚 烯烴具有水蒸氣透過率低等之高阻絕性，且雜質的溶出極 少，從衛生性優異的觀點，最適合作爲最內層I1。進而’ 環狀聚烯烴具有耐熱性或透明性，也適合於在需要以高壓 Φ 蒸汽等來滅菌，且期望能從外側目視內容物的醫療容器之 使用。 環狀聚烯烴可舉：環狀烯單體的開環聚合物及該開環 聚合物的氫添加物，進而，環狀烯單體的附加聚合物及能 與環狀烯單體與共聚的其他之單體的附加共聚物等。此等 當中，從耐熱性、機械性強度等觀點而言，以環狀烯單體 的開環聚合物的氫添加物爲佳。另外，從可以獲得低吸附 性的聚合物之觀點而言，以只由碳化氫所形成的環狀烯單 ❾ 體爲佳。 環狀烯單體並無特別限定，可舉：降冰片烯系單體及 單環式烯單體等。降冰片烯系單體繫於單體構造中具有源 自降冰片烯構造之單位的單體，具體而言，例如雙環 [2.2.1]七-2-烯（慣用名：降冰片烯）、三環[4.3.0.12,5] 十-3,7 -二嫌（慣用名：雙環戊二嫌）、7,8 -苯並三環 [4.3.0.12’5]十-3-烯（慣用名：甲烷四氫芴）及四環 [4.4.0.12’5·〗7’1 G]十二-3-烯（慣用名：四環十二烯）等。 另外，這些降冰片烯單體’也可以具有碳1〜3之碳化氫 -9- 200927083 基。單環式環狀烯單體，具體可舉：環己烯、環庚烯及環 辛烯等。此等環狀烯單體，可以使用單獨或2種以上。 環狀烯單體的開環聚合物，係於周知的開環聚合觸媒 的存在下，藉由置換反應而將環狀烯單體予以聚合所得 者。另外’環狀烯單體的開環聚合物的氫添加物，係藉由 周知的氫化觸媒而將開環聚合物予以氫化所獲得者。 另外’可與環狀烯單體附加共聚的其他單體，例如可 0 舉：乙烯、丙烯、1-丁烯、1-己烯等之碳數2〜20的α-烯。此等烯可以使用1種或2種以上。環狀烯單體的 附加（共）聚合物，可以藉由使用由周知的鈦、鍩化合物 與有機鋁化合物所形成的觸媒予以聚合來獲得。 在市售的環狀聚烯烴中，以環狀烯單體的附加（共） 聚合物而言’可舉：三井化學股份有限公司製阿貝爾（登 錄商標）、TICONA公司製TOPAS (登錄商標）等，以環 狀烯單體的開環聚合物之氫添加物而言，可舉：日本 Q ΖΕΟΝ股份有限公司製的 ΖΕΟΝΟΑ (登錄商標）及 ΖΕΟΝΕΧ (登錄商標）等。 作爲環狀聚烯烴，以玻璃態轉化溫度（以下，也有稱 爲Tg之情形）爲70°C〜18(TC者爲佳，以100。(：〜140°C 更佳，Tg未滿70 °C時，由多層體10所形成的醫療容器的 耐熱性低，會有不適合藉由高壓蒸汽等來滅菌的情形。另 一方面，T g如超過1 4 0 °c，則有多層體的成形性或薄片密 封性降低之虞。另外，此處玻璃態轉化溫度，係依據JIS K 7 121，藉由差異掃瞄熱量計（以下，稱爲DSC )所測量 -10- 200927083 的値，且係記載於製造公司的型錄、技術資料之値。 環狀聚烯烴的Tg，能在複數種的環狀聚烯烴中，藉 由適當的比率來將相溶性好者予以混合的方法等來任意地 調整。環狀聚烯烴的混合物的相溶性之程度，可以藉由 DSC來測量混合物的Tg而得知。相對於相溶性良好的混 合物之情形，只有1個Tg可被觀測到，在相溶性無法說 好的情形時，可以觀測到複數個Tg。如爲相溶性良好的 φ 混合物時，可以兼顧耐高壓蒸汽滅菌溫度之耐熱性與成形 性之目的，所以較佳。 另外，最內層11雖係由環狀聚烯烴所形成，但是在 不損及本發明的效果之範圍內，例如也可以在通常的使用 範圍內含有帶電防止劑、氧化防止劑、潤滑劑、防模糊 劑、紫外線吸收劑及中和劑等，在樹脂領域中一般所使用 的各種添加劑。 中間層12係鄰接前述之最內層11所形成的層，使用 ❹ 以二茂金屬觸媒爲代表的單一活化部位系觸媒所製造，且 密度爲0.860 g/cm3以上0.940 g/cm3未滿之直鏈型低密度 聚乙烯（以下，也有稱爲LLDPE的情形）爲主成分。另 外，此處所謂主成分，係指含有量爲50質量％以上。 使用單一活化部位系觸媒所製造的此種LLDPE，與環 狀聚烯烴的接著性優異之外，即使在藉由高壓蒸汽滅菌而 被暴露於高溫高濕條件的情形時，接著性之降低也少。因 此，藉由於由環狀聚烯烴所形成的最內層U鄰接設置以 此種LLDPE爲主成分的中間層12，透過此中間層12，可 200927083 以進一步良好且穩定地接著於其他層。另外，使用單一活 化部位系觸媒所製造的LLDPE，透明性也優異，即使在暴 露於高溫高濕條件的情形時，其劣化也少。由此等觀點而 言’具備有此種中間層12的多層體1〇，適合於需要藉由 高壓蒸汽來滅菌的醫療容器之形成。 作爲LLDPE，只要是使用單一活化部位系觸媒所製造 的密度0.860 g/cm3以上0.940 g/cm3未滿者，都可以合適 q 地使用’但是即使在此等之中，如使用密度0.900〜0.917 g/cm3者，可以獲得耐熱性更爲優異之多層體10或醫療容 器，即使在藉由121 t的高壓蒸汽來滅菌的情形時，也不 會產生任何障礙，以高壓蒸汽將由多層體1 0所形成的醫 療容器予以滅菌後的中間層1 2與最內層1 1的剝離強度之 降低會受到抑制。此處，LLDPE的密度未滿0_860 g/cm3 時，耐熱性有降低之虞。另一方面，LLDPE的密度在 0.940 g/cm3以上時，做爲容器之透明性或耐衝擊性有降低 ❹ 之虞。 另外，藉由單一活化部位系觸媒所製造的 LLDPE 中，藉由組成分析所測量的乙烯與α -烯的組成分佈廣 者，加工性或耐衝擊性優異，所以較爲理想。具備此種特 性的市售者，可以合適地使用日本聚乙烯股份有限公司製 的HARMOREX (登錄商標）、宇部興產股份有限公司製 的 YUMERIT (登錄商標）、股份有限公司 PRIME POLYMER製EVOLU (登錄商標）等。 另外，中間層1 2雖係以藉由單一活化部位系觸媒所 -12- 200927083 製造的LLDPE爲主成分，即含有50質量％以上，從柔軟 性的觀點，以65質量％以上，更佳爲80質量％以上含有 者，但是，在不阻礙與最內層11的接著性之範圍內，也 可以含有其他的聚乙烯或環狀聚烯烴。特別是，在30質 量％以下，更好爲2 5質量％以下的範圍來併用藉由單一活 化部位系觸媒所製造之比LLDPE密度更高的高密度聚乙 烯時，耐熱性提升，藉由高壓蒸汽滅菌之中間層12的接 0 著性的降低更受到抑制。另外，如此將其他的聚乙烯或環 狀聚烯烴與LLDPE倂用時，也有容易獲得外觀優異的多 層體1 〇之優點。 另外，中間層12也在不損及本發明的效果之範圍 內，例如可以在通常的使用範圍內含有：帶電防止劑、氧 化防止劑、潤滑劑、防模糊劑、紫外線吸收劑及中和劑 等，在樹脂領域中一般所使用的各種添加劑。 最外層13係由此多層體10來形成醫療容器時成爲最 Q 外側之層，且係含有高密度聚乙烯（以下，也有稱爲 HDPE的情形）所形成。 藉由將含有HDPE之層設置於最外層13,所獲得的多 層體10的耐熱性提升，可以形成因藉由高壓蒸汽之滅 菌，醫療容器的表面變形等特性劣化少的醫療容器。另 外，如第1圖的例子之薄膜狀的多層體10，多數係被捲繞 爲滾輪狀來保管、處理的情形，藉由於最外層13具備含 有HDPE之層，多層體10的耐阻隔性也優異。 HDPE雖然只要是密度爲0.940〜0.970 g/cm3者即可 -13- 200927083 合適地使用，但是此等當中’如使用密度爲0.94 5〜0.97 0 g/cm3者，可以獲得耐熱性、耐阻隔性更爲優異的多層體 10。另外，也可以倂用密度等之不同的複數種的HDPE。 另外，最外層13中之HDPE的合適含有量’雖然依 據HDPE的密度而不同，例如，在密度爲 0.945〜0.970 g/cm3的HDPE之情形時，如最外層13中20質量％以上 者，可以形成即使是基於121°C的高壓蒸汽之滅菌，特性 Q 劣化也少且有充分耐熱性的醫療容器。但是，爲了使實現 更穩定的耐熱性、耐阻隔性，最外層13的HDPE的含有 量，以30質量％以上爲佳，以70質量％以上較佳，以1〇〇 質量％更佳。 但是，爲了提高成形穩定性的目的，也有餘最外層13 倂用其他樹脂者，在該情形時，決定適當的HDPE的含有 量即可。此種其他樹脂，可舉HDPE以上的聚烯烴，可以 合適地使用直鏈型低密度聚乙烯、高壓法低密度聚乙烯等 〇 之聚乙烯樹脂。此等當中，如將高壓法低係度聚乙烯及 HDPE —同使用時，可以進一步提高最外層13的成形穩定 性。高壓法低係度聚乙烯，以其密度爲 0.910〜0.935 g/cm3者爲佳，以0.920〜0.935 g/cm3者更佳。 另外，最外層13也在不損及本發明的效果之範圍 內，在通常的使用範圍內含有：帶電防止劑、氧化防止 劑、潤滑劑、防模糊劑、紫外線吸收劑及中和劑等，在樹 脂領域中一般所使用的各種添加劑。另外，最外層13也 可以是施以藉由電子射線之架橋等之變性，以提升耐熱性 -14- 200927083 者。 多層體10的總厚度雖無特別限制，通常爲60〜1000 Μ Π1，如考慮多層體10的柔軟性或強度等’以100〜600 爲佳，以100〜400仁m更佳。 各層的厚度雖無特別限制，以最內層11爲5〜100 #m、最外層13爲5〜100以m爲佳。最內層11的厚度如 未滿5 μ m，有變得容易吸附所收容的藥劑之可能性，如 0 超過100/zm，多層體1〇的柔軟性，或從多層體來形 成醫療容器時的熱密封性有降低之虞。另外’最外層13 的厚度如未滿5//m’多層體10的耐熱性有降低之虞’如 超過1 00 A m，則有透明性降低之虞。 因此，在由3層所形成的多層體1 〇的情形時，以將 總厚度設爲60〜l〇〇〇//m’將最內層11設爲5〜100 #m、最外層設爲5〜100/zm、剩餘的設爲中間層12爲 佳。 Q 另外，在由3層所形成的多層體10爲薄膜之情形 時，以將最內層11設爲5〜1〇Mm、中間層12設爲50〜 300#m、最外層設爲5〜100"m爲佳。 第1圖的多層體係如前述般，爲由環狀聚烯烴所 形成的最內層11與含有HDPE之最外層13介由中間層12 而良好地接著之3層所形成者’雖具備作爲醫療容器用的 多層體10之充分的特性’但是以進一步賦予其他特性等 爲目的，於中間層12與最外層13之間設置1層以上的其 他層，來做成4層以上亦可。此種層’可舉：乙嫌-乙嫌 -15- 200927083 醇共聚物等之氣體阻隔性樹脂層、乙烯-醋酸乙烯共聚物 等之接著性樹脂層、含有氧化鐵之聚烯烴樹脂等之紫外線 遮蔽層 '由苯二甲基二胺與己二酸鹽等之α、ω-正鏈脂 肪族二氯基酸所得之MXD尼龍等之聚醯胺樹脂與由鈷鹽 所形成的氧氣吸收層等。 另外，多層體的型態，不單是如第1圖般形成爲薄膜 之多層體10，如之後詳細敘述般，也可以是以多層吹製成 0 形法（多層中空成形法）所形成的吹製成形體等立體形狀 的多層體。 本發明之醫療容器，係具備收容藥液的收容部之醫療 容器，至少收容部事由前述的多層體所形成。彼時，最內 層成爲收容部的內側，最外層成爲外側而配置。另外，醫 療容器通常在收容部之外，形成有成爲藥液的注入流出口 的埠口部。 以下，利用圖面來詳細說明本發明的醫療容器的具體 ❹ 例。 第2圖係收容部21與埠口部22以多層吹製成形法來 形成爲一體的醫療容器20。此醫療容器20的上部，爲形 成有吊掛孔之吊掛部23，下部的埠口部22，係於可以刺 穿注射針之圓柱狀的橡膠材的側面外周部裝著有以射出琢 形法設置可與最內層11熔接的合成樹脂之橡膠栓體22a 而被密封。 此醫療容器20可以藉由使用多層吹製成形機之通常 的多層吹製成形法來製造。即將多層型坯擠出，且以模具 -16- 200927083 夾入多層型坯後，於多層型坯中吹入清淨空氣即可。此處 之模具，可以藉由使用能將收容部21與埠口部22形成爲 一體者，來形成由中空狀的吹製成形體所形成的第2圖的 醫療容器20。另外，在以模具絞入多層型坯時，事先以清 淨空氣來前期吹氣，並且在關閉模具後，通過形成於模具 的真空孔來使模具內成爲負壓，則可以使模具的轉印精度 提高。 @ 另外，埠口部的形成法，在此種與收容部一同地以多 層吹製成形法來形成爲一體之方法外，例如可舉：如後述 的第3圖的例子般，將另外準備的圓筒構件熱密封於收容 部的方法，或藉由嵌入有圓筒構件的嵌入吹製成形與成形 同時地一體化之方法等。另外，在此等使用圓筒構件的情 形時，於圓筒構件裝著橡膠栓體22a來予以密封之型態 外，如之後以第3 ( B )所示來詳細說明般，也可以是使 用於將橡膠栓裝塡於圓筒構件後，進而以環狀的蓋構件來 φ 壓抑橡膠栓的周緣部，藉由超音波等來使蓋構件與圓筒構 件熔接之方法來密封的型態。 第3(A)圖係表示具備：藉由薄膜的熱板成形所形 成的收容部31;及由圓筒構件所形成，且可以藉由橡朦栓 體32a被熱密封來予以密封的埠口部32的醫療容器30。 此醫療容器30的收容部31’係由二片第4圖的薄膜成形 品10’疊合，且周緣部33被熱密封所形成。 即在製造此醫療容器30的情形時，首先，藉由真空 成形或壓空成形等之熱板成形，於第1圖的薄膜狀的多層 -17- 200927083 體1 〇的中央部形成沿著收容部31的內形之凹部，來獲得 第4圖所示之薄膜成形品1〇’。接著，準備2片之此薄膜 成形品10’，以凹部彼此相向之方向予以疊合。而且，於 特定的位置配置圓筒構件，將2騙得薄膜成形品10’的周 緣部予以熱密封。熱密封溫度，係依據多層體10的總厚 度而不同，雖無特別限定，以大約150〜280 °C爲佳。另 外，於熱密封後，因應需要，將周緣部予以修整亦可。如 0 依據此方法，可以同時進行收容部31的形成與藉由圓筒 構件的熱密封之埠口部32的形成，來製造第3(A)圖的 醫療容器30。 另外，收容部31的形成與埠口部32的形成，也可以 別的工程來進行。 作爲形成埠口部32的圓筒構件的材質，基於與收容 部31的熱密封性良好的關係，與多層體的最內層u 同樣’以環狀聚烯烴爲合適，但是，只要是與收容部31 φ 能夠液密地熱密封者，並不限定爲環狀聚烯烴，也可以使 用藉由單一活化部位系觸媒所製造的LLDPE、與中間層 1 2相同的組成物等。另外’也可以是將能夠熱密封的樹脂 使用於圓筒構件的熱密封面之多層者。另外，也可以代替 由圓筒構件與橡膠栓體32a所形成，如第3(B)圖所示 般，將橡膠栓32b裝塡於圓筒構件後，以環狀的蓋構件 32c按壓橡膠栓32b的周緣部，將蓋構件32c與圓筒構件 藉由超音波等來熔接以形成此處之埠口部32。 第5圖係具備··如第1圖的薄膜狀的多層體1〇形成 -18- 200927083 爲袋狀之收容部41 ;及由圓筒構件所形成的埠口窗 所謂薄膜袋型之醫療容器40。 此例之醫療容器40係使用以多層充氣法等形 狀之多層體，將其兩端不與以熱密封來形成收容部 於其一端的特定位置熱密封圓筒構件來作爲埠口部 另一端形成吊掛部之方法來製造。兩端部的熱密封 構件的熱密封，可以同時進行，也可以個別工程來 U 另外，代替使用圓筒狀的多層體，也可以使用2片 圖的多層體1 〇，將彼等疊合後，以將周緣部予以熱 方法來形成收容部。 另外，此例中’埠口部42係藉由：以環狀聚 單一活化部位系觸媒製造的LLDPE等所形成的 件；及可以刺穿注射針之橡膠栓42a ;及按壓橡膠 的周緣部之環狀的蓋構件42b而被密封。 如依據以上說明之醫療容器，至少收容部係由 Q 由環狀聚烯烴所形成的最內層；及以使用單一活化 觸媒所製造的直鏈型低密度聚乙烯爲主成分之中間 含有高密度聚乙烯的最外層之多層體所形成，各層 好地接著’且具有衛生性，進而耐熱性優異，在高 滅菌之情形，透明性、剝離強度等之特性劣化少。 另外，作爲醫療容器的型態，並不限定爲具備 容部的型態，例如，也可以如第6圖所示般，藉由 通的隔壁密封部52來將收容部51區隔爲複數個， 別收容複數種的藥液之複室醫療容器50。 ;42之 成爲筒 41，且 42，於 與圓筒 進行。 如第1 密封之 烯烴或 圓筒構 栓 42a 具備： 部位系 層；及 可以良 壓蒸汽 1個收 可以連 能夠個 -19-[Technical Field] The present invention relates to a multilayer body for a medical container and a medical container having the drug solution accommodating portion formed by the multilayer body for the medical container. [Prior Art] As a medical container made of a resin used in the medical field, there are an ampoule 0 (a ampule), a vial (vial), an injection container, an infusion bag formed of a thin film, and the like. Further, as the resin, a polyolefin such as polyethylene or polypropylene, a styrene-based elastomer, a vinyl chloride resin, an ethylene-vinyl acetate copolymer, or a cyclic polyolefin is used. Among these resins, polyethylene is widely used in medical containers because it is hygienic and soft, and does not generate toxic gases when burned, but on the other hand, it is connected to medical liquids in medical containers. In the liquid portion, when polyethylene is used, the polyethylene in the chemical solution adsorbs a specific II agent such as fat-soluble vitamin, and it is found that the concentration of the specific drug may decrease during storage. Therefore, it is possible to suppress the decrease in the effectiveness of the drug due to the adsorption or absorption of a specific drug, and it is excellent in transparency, heat resistance, hygiene, and the like, and further has a highly resistant cyclic polyolefin such as a low water vapor transmission rate. Materials used as medical containers are gradually being widely used. In a medical container using a cyclic polyolefin, a pre-filled syringe in which a pharmaceutical agent is previously filled in a syringe container is being popularized. Further, Patent Document 1 discloses a multilayered medical container in which a synthetic resin layer or a barrier layer is combined with a cyclic polyolefin layer formed of a thermoplastic resin-saturated icing-200903083 enelen monomer. Patent Document 2 discloses that a multilayer film including a surface layer, a soft layer, a barrier layer, and a sealing layer is used, and a cyclic polyorganism hydrocarbon and an ethylene-α-ene copolymer are used for the barrier layer, and ethylene-α is used for the other layer. A medical container containing an olefin copolymer as a main component. Patent Document 3 discloses that a linear layer having a specific melting point and a Vicat softening point is laminated on one side or both sides of a tantalum layer formed of a resin such as a cyclic polyolefin. A laminated film of layer B formed of low-density polyethylene and a medical container using the same. Further, Patent Document 4 discloses that a base material layer containing a polyolefin-based resin containing a specific melting point as a main component is laminated with a cyclic polyolefin-based resin having a specific glass transition temperature as a main component. A medical container for laminating a film of a layer. [Patent Document 1] Japanese Patent No. 3227709 〇 [Patent Document 2] International Patent Publication No. 03/0973 5 5 pamphlet [Patent Document 3] Japanese Patent Laid-Open No. 2004- 1 67800 (Patent Document 4) Japanese Patent [Problems to be Solved by the Invention] However, as described in paragraph 0027 of Patent Document 1 or paragraph 0004 of Patent Document 2, the cyclic polyolefin has disadvantages of poor adhesion. . Therefore, in the case of producing the multilayer film of Patent Document 1, when the cyclic polyolefin layer -5 - 200927083 _ is laminated with other layers, it is necessary to use an adhesive. However, in the use of the multilayer film, there is a possibility that the component derived from the adhesive is released. Therefore, if such a multilayer film is used for a medical container, particularly for use in the vicinity of the drug solution, it is not suitable from the viewpoint of hygiene. In the technique of Patent Document 2, in order to improve the adhesion of the cyclic polyolefin, a vinyl-α-ene copolymer is mixed with a cyclic polyolefin to form a barrier layer. However, when the ethylene-α-ene copolymer is mixed, the barrier property of the barrier layer is lowered, and the agent is absorbed by the layer adjacent to the barrier layer. Further, when it is desired to improve the barrier property and thicken the barrier layer, there is a problem that the flexibility is lowered. Further, the medical container described in Patent Document 3 or 4 is insufficient in heat resistance and cannot satisfy the material of a medical container which is required to be sterilized by high-pressure steam. Further, the laminated film disclosed in Patent Document 3 or 4 has a disadvantage that the barrier property is not good. The present invention has been made in view of the above circumstances, and it is an object of the invention to provide that the innermost layer and the other layer formed of a cyclic polyolefin can be satisfactorily adhered without using an adhesive, and the heat resistance is also excellent, and in the case of a film A multilayer container for a medical container which is excellent in barrier properties, and a medical container formed of a multilayer body for a medical container, and which is sterilized by high-pressure steam or the like, and which has little deterioration in characteristics such as transparency and peel strength. [Means for Solving the Problem] The multilayer body for a medical container according to the present invention is a multilayer body for a medical container which is used in a medical container, and is characterized in that it has at least a maximum of __ formed of a cyclic polyolefin. An inner layer; and an intermediate layer formed by abutting the innermost layer and having a linear low-density polyethylene produced by using a single-site catalyst; and a high-density polyethylene The outermost layer. The cyclic polyolefin is preferably a hydrogen addition of a ring-opening polymer of a cyclic olefin monomer. Q The linear low-density polyethylene has a density of 0.860 g/cm3 or more and less than 0.940 g/cm3. The density of the aforementioned high-density polyethylene is 〇.94 〇 to 0.970 g/cm3. The outermost layer is a mixture of the aforementioned high-density polyethylene and high-pressure process low-density polyethylene, or is formed only of the aforementioned high-density polyethylene. The multilayer body for a medical container according to the present invention has a total thickness of 60 to 1000 μm and is composed of the innermost layer having a thickness of 5 to 100/m and the intermediate layer and the outermost layer having a thickness of 5 to ΙΟΟμπι. The third layer is formed. The medical container according to the present invention is a medical container including a housing portion for storing a chemical liquid, characterized in that at least the housing portion is formed of the multilayer body for a medical container. In this case, the multilayer body for a medical container may be a blow molded body. [Effect of the Invention] According to the present invention, it is possible to provide an inner layer formed of a ring-shaped polyolefin of the type 200927083 without using an adhesive, which is excellent in heat resistance and good in the case of a film. A multilayer container for a medical container which is excellent in barrier properties, and a medical container formed of a multilayer body for a medical container, which is sterilized by high-pressure steam, and which has little deterioration in characteristics such as transparency and peel strength. [Embodiment] 0 Hereinafter, the present invention will be described in detail. The multilayer body for a medical container according to the present invention is used for forming a medical container, and is particularly suitable for use in forming a housing portion for storing a chemical solution in a medical container, and has at least an innermost layer formed of a cyclic polyolefin. And an intermediate layer formed by adjoining the innermost layer and having a linear low-density polyethylene produced by using a single-site catalyst; and an outer layer containing high-density polyethylene . Fig. 1 is a view showing a multilayer body for medical containers (referred to as a multilayer body under G) according to an example of the present invention. The multilayer body of this example is composed of: an innermost layer 11 formed of a cyclic polyolefin; and an intermediate layer 12 mainly composed of a linear low-density polyethylene produced by using a single activated site-based catalyst. And the outermost layer 13 containing high-density polyethylene is formed by three layers of sequential lamination, and is formed into a film by a multi-layer expansion molding method such as air cooling or water cooling, a multilayer T-die molding method, or the like. Further, in the present invention, the film and the sheet are collectively referred to as a film. The innermost layer 11 is formed by a loop-like polyene hydrocarbon when it is formed into a medical container from the multilayer body 10, and is directly in contact with a chemical solution or the like contained in the medical container. In the cyclic polyolefin, since the adsorption or absorption of the drug is small, the medical container is formed by forming the layer formed of the cyclic polyolefin as the multilayer body 10 of the innermost layer 11, and the effectiveness of the contained chemical solution can be suppressed from being lowered. Further, the cyclic polyolefin has high barrier property such as low water vapor transmission rate and extremely little elution of impurities, and is most suitable as the innermost layer I1 from the viewpoint of excellent hygiene. Further, the cyclic polyolefin has heat resistance and transparency, and is also suitable for use in a medical container which is required to be sterilized by high pressure Φ steam or the like and which is expected to visually view the contents from the outside. The cyclic polyolefin may be a ring-opening polymer of a cyclic olefin monomer and a hydrogen additive of the ring-opening polymer, and further, an additional polymer of a cyclic olefin monomer and a copolymerizable with a cyclic olefin monomer. Additional copolymers of other monomers, and the like. Among these, from the viewpoints of heat resistance, mechanical strength, and the like, a hydrogen additive of a ring-opening polymer of a cyclic olefin monomer is preferred. Further, from the viewpoint of obtaining a polymer having low adsorptivity, a cyclic alkene monomethane formed only of hydrogen carbide is preferred. The cyclic olefin monomer is not particularly limited, and examples thereof include a norbornene-based monomer and a monocyclic olefin monomer. The norbornene-based single system has a monomer derived from a unit of a norbornene structure in a monomer structure, specifically, for example, bicyclo [2.2.1] hep-2-ene (common name: norbornene), three Ring [4.3.0.12,5] Ten-3,7-two suspects (common name: dicyclopentane), 7,8-benzotricyclo[4.3.0.12'5]dec-3-ene (common name: Methane tetrahydroanthracene) and tetracyclic [4.4.0.12'5·]7'1 G]dodec-3-ene (common name: tetracyclododecene). Further, these norbornene monomers ' may also have a carbon hydride-9-200927083 group of carbons 1-3. Specific examples of the monocyclic olefin monomer include cyclohexene, cycloheptene, and cyclooctene. These cyclic olefin monomers may be used alone or in combination of two or more. The ring-opening polymer of the cyclic olefin monomer is obtained by polymerizing a cyclic olefin monomer by a substitution reaction in the presence of a known ring-opening polymerization catalyst. Further, the hydrogen addition of the ring-opening polymer of the cyclic olefin monomer is obtained by hydrogenating the ring-opening polymer by a known hydrogenation catalyst. Further, the other monomer which can be additionally copolymerized with the cyclic olefin monomer may, for example, be an α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene or 1-hexene. These olefins may be used alone or in combination of two or more. The additional (co)polymer of the cyclic olefin monomer can be obtained by polymerization using a catalyst formed of a well-known titanium, ruthenium compound and an organoaluminum compound. In the case of the commercially available cyclic polyolefin, the addition (co)polymer of the cyclic olefin monomer is exemplified by Abel (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. and TOPAS (registered trademark) manufactured by TICONA Co., Ltd. In the case of the hydrogen addition of the ring-opening polymer of the cyclic olefin monomer, ΖΕΟΝΟΑ (registered trademark) and ΖΕΟΝΕΧ (registered trademark) manufactured by J. Co., Ltd., Japan, etc., may be mentioned. As the cyclic polyolefin, the glass transition temperature (hereinafter, also referred to as Tg) is 70 ° C to 18 (the TC is preferably 100, which is more preferable, and the Tg is less than 70 °). In the case of C, the medical container formed of the multilayer body 10 has low heat resistance and may be unsuitable for sterilization by high-pressure steam or the like. On the other hand, if the T g exceeds 140 ° C, the multilayer body is formed. In addition, the glass transition temperature here is based on JIS K 7 121, measured by a differential scanning calorimeter (hereinafter referred to as DSC), and is measured by -10-200927083. It is described in the catalogue and technical data of the manufacturing company. The Tg of the cyclic polyolefin can be arbitrarily mixed in a plurality of cyclic polyolefins by a suitable ratio of a good compatibility. The degree of compatibility of the mixture of cyclic polyolefins can be known by measuring the Tg of the mixture by DSC. Only one Tg can be observed with respect to the mixture with good compatibility, and the compatibility cannot be obtained. When you say a good situation, you can observe a number of Tg. In the case of a good φ mixture, it is preferable to achieve both the heat resistance and the formability of the autoclave sterilization temperature. Further, although the innermost layer 11 is formed of a cyclic polyolefin, the present invention is not impaired. In the range of the effect, for example, a charge preventing agent, an oxidation preventive agent, a lubricant, an anti-fuzzing agent, an ultraviolet absorber, a neutralizing agent, etc. may be contained in a usual range of use, and various additives generally used in the field of resins may be used. The intermediate layer 12 is a layer formed by abutting the innermost layer 11 described above, and is made of a single active site catalyst represented by a metallocene catalyst, and has a density of 0.860 g/cm 3 or more and 0.940 g/cm 3 . The linear low-density polyethylene (hereinafter also referred to as LLDPE) is a main component. The main component herein means a content of 50% by mass or more. It is produced by using a single activated site catalyst. Such an LLDPE is excellent in adhesion to a cyclic polyolefin, and even when it is exposed to high-temperature and high-humidity conditions by autoclaving, the decrease in adhesion is small. Therefore, the intermediate layer 12 mainly composed of such an LLDPE is provided adjacent to the innermost layer U formed of the cyclic polyolefin, and the intermediate layer 12 can be passed through the intermediate layer 12 to further and stably follow the other layers. LLDPE produced by using a single activated site-based catalyst is also excellent in transparency, and has little deterioration even when exposed to high-temperature and high-humidity conditions. From this point of view, 'there is such an intermediate layer 12 The multilayer body is suitable for the formation of a medical container that needs to be sterilized by high-pressure steam. As the LLDPE, as long as the density of 0.860 g/cm3 or more and 0.940 g/cm3 is less than that produced by using a single activated site catalyst, It can be suitably used, but even in such a case, if a density of 0.900 to 0.917 g/cm3 is used, a multilayer body 10 or a medical container which is more excellent in heat resistance can be obtained, even by a high pressure steam of 121 t. In the case of sterilization, there is no obstacle, and the peeling strength of the intermediate layer 12 and the innermost layer 1 1 after the medical container formed by the multilayer body 10 is sterilized by high pressure steam will be lowered. Suppressed. Here, when the density of the LLDPE is less than 0_860 g/cm3, the heat resistance is lowered. On the other hand, when the density of LLDPE is 0.940 g/cm3 or more, the transparency or impact resistance of the container is lowered. Further, in the LLDPE produced by a single activation site catalyst, the composition distribution of ethylene and α-olefin measured by the composition analysis is excellent, and the workability and impact resistance are excellent, which is preferable. For those who have such a characteristic, HARMONEX (registered trademark) manufactured by Nippon Polyethylene Co., Ltd., YUMERIT (registered trademark) manufactured by Ube Industries, Ltd., and EVOLU manufactured by PRIME POLYMER Co., Ltd. can be used as appropriate. Trademarks) and so on. In addition, the intermediate layer 12 is mainly composed of LLDPE produced by a single activation site catalyst -12-200927083, that is, 50% by mass or more, and more preferably 65 mass% or more from the viewpoint of flexibility. It is contained in an amount of 80% by mass or more, but may contain other polyethylene or a cyclic polyolefin insofar as it does not inhibit the adhesion to the innermost layer 11. In particular, when 30 mass% or less, more preferably 25 mass% or less, a high density polyethylene having a higher density than LLDPE produced by a single activation site catalyst is used, heat resistance is improved by The decrease in the susceptibility of the intermediate layer 12 of autoclaving is further suppressed. Further, when other polyethylene or cyclic polyolefin is used in combination with LLDPE, there is an advantage that a multi-layered body having an excellent appearance can be easily obtained. Further, the intermediate layer 12 is also within the range of not impairing the effects of the present invention, and may contain, for example, a charge preventing agent, an oxidation preventing agent, a lubricant, an anti-fuzzing agent, an ultraviolet absorber, and a neutralizing agent within a usual range of use. Etc., various additives generally used in the field of resins. The outermost layer 13 is formed as a layer on the outermost side of the Q when the medical container is formed by the multilayer body 10, and is made of high-density polyethylene (hereinafter also referred to as HDPE). By providing the layer containing the HDPE to the outermost layer 13, the heat resistance of the obtained multilayer body 10 is improved, and a medical container having little deterioration in characteristics such as surface deformation of the medical container by sterilization by high-pressure steam can be formed. In addition, in the case of the film-form multilayer body 10 of the example of Fig. 1, many of them are wound and stored in a roll shape, and the outermost layer 13 is provided with a layer containing HDPE, and the barrier property of the multilayer body 10 is also Excellent. Although HDPE can be suitably used as long as it has a density of 0.940 to 0.970 g/cm3, it can be suitably used, for example, if the density is 0.94 5 to 0.97 0 g/cm3, heat resistance and barrier resistance can be obtained. More excellent multilayer body 10. In addition, a plurality of HDPEs having different densities or the like may be used. In addition, the proper content of HDPE in the outermost layer 13 varies depending on the density of the HDPE. For example, in the case of HDPE having a density of 0.945 to 0.970 g/cm3, as in the outermost layer 13, 20% by mass or more, Even in the case of sterilization based on high pressure steam at 121 ° C, a medical container having a small deterioration in characteristic Q and sufficient heat resistance is formed. However, in order to achieve more stable heat resistance and barrier properties, the content of HDPE in the outermost layer 13 is preferably 30% by mass or more, more preferably 70% by mass or more, and still more preferably 1% by mass. However, in order to improve the forming stability, the outermost layer 13 may be made of other resin. In this case, the content of the appropriate HDPE may be determined. The other resin may be a polyolefin of HDPE or higher, and a polyethylene resin such as a linear low-density polyethylene or a high-pressure low-density polyethylene may be suitably used. Among these, if the high-pressure method low-density polyethylene and HDPE are used together, the formation stability of the outermost layer 13 can be further improved. The low-pressure polyethylene having a high pressure method is preferably a density of 0.910 to 0.935 g/cm3, more preferably 0.920 to 0.935 g/cm3. Further, the outermost layer 13 contains, within a normal range of use, a charge preventing agent, an oxidation preventing agent, a lubricant, an anti-fuzzing agent, an ultraviolet absorber, and a neutralizing agent, etc., insofar as the effects of the present invention are not impaired. Various additives generally used in the field of resins. Further, the outermost layer 13 may be subjected to denaturation by an electron beam bridge or the like to improve heat resistance -14-200927083. The total thickness of the multilayer body 10 is not particularly limited, but is usually 60 to 1000 Μ , 1, and the flexibility or strength of the multilayer body 10 is considered to be preferably 100 to 600, more preferably 100 to 400 Å. The thickness of each layer is not particularly limited, and the innermost layer 11 is 5 to 100 #m, and the outermost layer 13 is preferably 5 to 100 m. If the thickness of the innermost layer 11 is less than 5 μm, there is a possibility that the contained drug can be easily adsorbed, for example, 0 exceeds 100/zm, the flexibility of the multilayer body 1〇, or when the medical container is formed from the multilayer body. The heat sealability is reduced. Further, if the thickness of the outermost layer 13 is less than 5/m, the heat resistance of the multilayer body 10 is lowered, e.g., if it exceeds 100 Å, the transparency is lowered. Therefore, in the case of the multilayer body 1 formed of three layers, the innermost layer 11 is set to 5 to 100 #m, and the outermost layer is set to have a total thickness of 60 to 1 〇〇〇//m'. 5 to 100/zm, and the remaining intermediate layer 12 is preferable. Further, when the multilayer body 10 formed of three layers is a film, the innermost layer 11 is set to 5 to 1 〇Mm, the intermediate layer 12 is set to 50 to 300 #m, and the outermost layer is set to 5 to 100"m is better. As described above, the multilayer system of Fig. 1 is formed by a combination of the innermost layer 11 made of a cyclic polyolefin and the outermost layer 13 containing HDPE, which is formed by the intermediate layer 12 and is well formed. For the purpose of further imparting other characteristics and the like for the purpose of further imparting other characteristics and the like, one or more layers may be provided between the intermediate layer 12 and the outermost layer 13 to form four or more layers. Such a layer can be exemplified by a gas barrier resin layer such as an alcohol copolymer, an adhesive resin layer such as an ethylene-vinyl acetate copolymer, or a polyolefin resin containing iron oxide. The masking layer 'polyamide resin such as MXD nylon obtained from α,ω-n-chain aliphatic dichloro acid such as dimethylenediamine and adipate, and an oxygen absorbing layer formed of a cobalt salt . Further, the shape of the multilayer body is not limited to the multilayer body 10 formed as a film as shown in Fig. 1, and as described later in detail, it may be a blow formed by a multilayer blow forming a 0-shaped method (multilayer hollow molding method). A multilayer body having a three-dimensional shape such as a molded body. The medical container of the present invention is a medical container including a housing portion for storing a chemical liquid, and at least the housing portion is formed of the above-described multilayer body. At that time, the innermost layer becomes the inner side of the accommodating portion, and the outermost layer is disposed outside. Further, the medical container is usually formed with a mouth portion which is an injection flow outlet for the chemical liquid, other than the accommodating portion. Hereinafter, a specific example of the medical container of the present invention will be described in detail using the drawings. Fig. 2 is a medical container 20 in which the accommodating portion 21 and the mouth portion 22 are integrally formed by a multi-layer blow molding method. The upper portion of the medical container 20 is a hanging portion 23 in which a hanging hole is formed, and the lower mouth portion 22 is attached to the outer peripheral portion of the side surface of the cylindrical rubber material that can pierce the injection needle to emit a dome shape. The rubber plug 22a of the synthetic resin which can be welded to the innermost layer 11 is sealed. This medical container 20 can be manufactured by a conventional multi-layer blow molding method using a multi-layer blow molding machine. That is, the multi-layer parison is extruded, and after the multi-layer parison is sandwiched by the mold -16-200927083, the clean air is blown into the multi-layer parison. Here, the medical container 20 of Fig. 2 formed of a hollow blow-molded body can be formed by using the accommodating portion 21 and the mouth portion 22 integrally. In addition, when the multi-layer parison is twisted by the mold, the air is blown in advance with clean air, and after the mold is closed, the vacuum is formed in the mold to make the inside of the mold a negative pressure, so that the transfer precision of the mold can be made. improve. In addition, the method of forming the mouth portion is formed by a multi-layer blow molding method together with the accommodating portion, and for example, it is prepared separately as in the example of Fig. 3 to be described later. A method in which the cylindrical member is heat-sealed to the accommodating portion, or a method in which the cylindrical member is embedded and blown into shape and integrated simultaneously with the forming. Further, in the case where the cylindrical member is used, the cylindrical member may be sealed by the rubber plug 22a, and may be described in detail as shown in the third (B). After the rubber plug is attached to the cylindrical member, the peripheral portion of the rubber plug is φ-repressed by the annular cover member, and the cover member and the cylindrical member are welded by ultrasonic waves or the like to seal the shape. Fig. 3(A) is a view showing a housing portion 31 formed by hot plate forming of a film, and a mouthpiece formed of a cylindrical member and sealed by heat sealing of the rubber plug 32a. The medical container 30 of the portion 32. The accommodating portion 31' of the medical container 30 is formed by laminating two sheets of the film-formed product 10' of Fig. 4, and the peripheral portion 33 is formed by heat sealing. In other words, in the case of manufacturing the medical container 30, first, a hot plate forming such as vacuum forming or pressure forming is used to form a central portion of the film-like multilayer -17-200927083 in the first drawing. The concave portion of the inner portion of the portion 31 is used to obtain the film-formed product 1' shown in Fig. 4. Next, two sheets of the film-formed product 10' are prepared, and the concave portions are superposed on each other in the direction in which they face each other. Further, the cylindrical member is placed at a specific position, and the peripheral portion of the film-formed product 10' is entangled to be heat-sealed. The heat sealing temperature differs depending on the total thickness of the multilayer body 10, and is not particularly limited, and is preferably about 150 to 280 °C. In addition, after heat sealing, the peripheral portion may be trimmed as needed. According to this method, the medical container 30 of Fig. 3(A) can be manufactured by simultaneously forming the accommodating portion 31 and forming the mouth portion 32 by heat sealing of the cylindrical member. Further, the formation of the accommodating portion 31 and the formation of the mouth portion 32 may be performed by another project. The material of the cylindrical member forming the crotch portion 32 is preferably a cyclic polyolefin similar to the innermost layer u of the multilayer body, based on a good heat seal property with the accommodating portion 31. However, as long as it is contained and contained The portion 31 φ can be heat-sealed in a liquid-tight manner, and is not limited to a cyclic polyolefin. LLDPE produced by a single activation site-based catalyst, a composition similar to the intermediate layer 12, or the like can be used. Further, a resin which can be heat-sealed may be used for a plurality of layers of the heat sealing surface of the cylindrical member. Alternatively, instead of being formed of the cylindrical member and the rubber plug 32a, as shown in Fig. 3(B), after the rubber plug 32b is attached to the cylindrical member, the rubber stopper is pressed by the annular cover member 32c. At the peripheral portion of 32b, the cover member 32c and the cylindrical member are welded by ultrasonic waves or the like to form the mouth portion 32 here. Fig. 5 is a film-shaped multi-layered body 1 formed in Fig. 1 and formed into a bag-shaped accommodating portion 41; and a sputum window formed of a cylindrical member. 40. In the medical container 40 of this example, a multilayer body having a shape such as a multi-layer inflation method is used, and the both ends are not heat-sealed at a specific position where the accommodating portion is formed at one end thereof by heat sealing to form the other end of the gargle portion. The method of hanging the part is to manufacture. The heat sealing of the heat-sealing members at both ends may be performed at the same time, or may be carried out separately. Alternatively, instead of using a cylindrical multilayer body, it is also possible to use two layers of the multilayer body 1 〇 to laminate them. The heat storage method is used to form the accommodating portion. Further, in this example, the 'mouth portion 42' is a member formed of LLDPE or the like which is produced by a ring-shaped single activation site-based catalyst; and a rubber plug 42a which can pierce the injection needle; and a peripheral portion of the rubber The annular cover member 42b is sealed. According to the medical container described above, at least the accommodating portion is composed of an innermost layer formed of a cyclic polyolefin and a linear low-density polyethylene produced by using a single activating catalyst as a main component. The multilayered body of the outermost layer of the density polyethylene is formed, and each layer is well followed and has hygienic properties, and is excellent in heat resistance. In the case of high sterilization, the properties such as transparency and peel strength are less deteriorated. Further, the shape of the medical container is not limited to the shape including the volume. For example, as shown in Fig. 6, the accommodating portion 51 may be partitioned into plural numbers by the partition wall sealing portion 52 that is opened. , Do not accommodate a plurality of medical fluids in the multi-chamber medical container 50. 42 becomes the cylinder 41, and 42, is carried out with the cylinder. For example, the first sealed olefin or cylindrical plug 42a has: a portion of the layer; and a good pressure steam can be connected to one can be connected -19-
GG
200927083 第6圖的複室醫療容器50，係沿著形成爲袋形 部51之寬度方向設置有隔壁密封部52 ’收容部5】 成第1收容部51a與第2收容部51b。隔壁密封部 複室醫療容器50之使用時’使用者藉由從外部S 收容部51a或第2收容部51b而予以剝離，將第1 51a內的藥液與第2收容部51b內的藥液予以混合 隔壁密封部5 2的形成方法並無限制，例如， 部5 1的形成時，在被施以熱密封的情形時，在其 予以熱密封來形成亦可。另外，在熱密封之外，以 封等之周知的密封方法來另外進行亦可。進而，1± 成在以吹製成形來製造收容部51之情形時，於吵 時所使用的模具設置形成隔壁密封部52用的機精 在吹製成形的同時，可以形成隔壁密封部52。 進而，雖然省略圖示，於本發明之醫療容器， 側’特別是收容部的外側，可以因應需要設置保_ 的遮光層。適合遮光層的材料，例如可以舉：鋁箱 屬箔、鋁蒸鏟薄膜、金屬箔與合成樹脂薄膜的貼爸 含有顏料的合成樹脂薄膜等。在此等遮光層之中， 銘蒸鍍薄膜等，不單遮光性，也具有防濕性、耐拍 吸水性等’從提高收容於醫療容器的藥液的長期保 觀點等而言’較爲合適。另外，也可將此種遮光層 可從醫療容器剝離，做成於醫療容器使用時，可以 來目視藥液。 以上’雖作爲收容於本發明的醫療容器之藥 的收容 被分割 52係於 壓第1 收容部 ► 於收容 同時， 脈衝密 可以做 製成形 ，以便 於其外 藥液用 等之金 薄膜、 鋁箔或 性、非 存性之 設置爲 從外側 ，以藥 -20- 200927083 液爲例而做說明’但是’不單是藥液’也可以是由抗生素 物質等粉劑所形成的藥劑。另外’具體的藥液’可舉：生 理用食鹽水、循環器系統藥劑、造影劑及抗菌劑等作爲注 射劑使用的藥液。但是’並不限定爲這些。 [實施例] 以下，舉出實施例來具體地說明本發明’但是’本發 明並不限定爲以下的實施例。 [實施例1] 如以下般製造塡充有1 00 ml的水之第2圖的醫療容 器20 〇 首先，藉由使用多層吹製成形機的多層吹製成形法， 一體形成由厚度的最內層、及厚度250/zm的中間 層、及厚度20/ζιη的最外層被依序層積的3層構造之吹製 成形體所形成的收容部21與埠口部22。接著，從埠口部 22對收容部21內塡充水100 ml後，將橡膠栓體22a熱密 封於埠口部22而將醫療容器20予以密封。作爲橡膠栓體 22a，係使用於橡膠栓的外周部以射出成形法設置有由： 依據ISO 1133，280 °C中之熔解流動率（以下，稱爲 [MFR]。另外，實施例、比較例中，MFR測定時之負荷全 部爲21.18N。）爲17g/10分鐘、玻璃態轉化溫度爲136 °C之環狀聚烯烴「ZEONEX (曰本ΖΕΟΝ株式會社製）」 (以下，稱爲「COP1」。）所形成的層者。 -21 - 200927083 另外，最內層係使用將COP 1、及依據ISO 1133，280 °C中之MFR爲20g/10分鐘、玻璃態轉化溫度爲102°C之 環狀聚烯烴「ZEONOA (日本ΖΕΟΝ株式會社製）」（以 下，稱爲「COP2」。）以1 : 1的質量比混合的環狀聚烯 烴的混合物。此混合的環狀聚烯烴的Tg，只是觀測到1 個，爲U9°C。 中間層係使用將藉由單一活化部位系觸媒所製造的 ^ LLDPE (以下，也稱爲單一活化部位系LLDPE)，且190 °C 中之 MFR 爲 lg/ΙΟ 分鐘、密度 0.906 g/cm3 之 HDPE 「HARMOREX (日本聚乙烯株式會社製）」：及190 °C中 之 MFR 爲 3.5g/10 分鐘、密度 0.956 g/cm3 之 HDPE 「NOVATEC(日本聚乙烯株式會社製）」以8:2的質量 比予以混合者。 最外層係使用190°C中之MFR爲3.5g/l 0分鐘、密度 0.95 5 g/cm3之 HDPE「NO VATEC (日本聚乙烯株式會社 ❿ 製）」。 針對如此獲得而塡充有水之第2圖的醫療容器20,藉 由噴灑式高壓蒸汽滅菌，以121 °C、30分鐘進行高壓蒸汽 滅菌處理，如下述評估其前後的特性，將評估結果表示於 表中。 另外，在實施例及比較例中，耐阻隔性及成形穩定性 的評估，只在由薄膜成形，且形成了收容部的例子之情形 進行，如實施例1般，由多層吹製成形來形成收容部的情 形時，並不進行評估。 -22- 200927083 (評估方法） (〇耐阻隔性 將lOcmxlOcm的2片的多層體，以其最外層彼此相 接的方式予以疊合，於其上加上98N/100cm2的負荷，保 持601：、24小時。之後，冷卻至室溫，去除負荷後’將2 片的薄膜予以剝離。針對此時之剝離狀態，以以下的2階 段來評估。 〇：容易剝離 X :剝離時有阻力 (2 )剝離強度 由高壓蒸汽滅菌前後的醫療容器切出寬度15 mm的長 方形的樣品S，模式性地表示於第7 ( A )圖，以拉伸速度 300 mm/分鐘來測定最內層11與中間層12間之依據JIS K68 54-3之T形剝離強度。試驗係藉由拉伸試驗機來進 行。圖中符號P，係表示拉伸試驗機的夾頭。 另外，如第7 ( A )圖所示般，於將樣品S做成只有 其最內層11於破斷部V破斷的狀態上，首先，如第7 (B)圖的平面圖所示般，於由醫療容器所切出的樣品S 的寬度方向的兩端部，於相互相向的2處所設置切痕C， 如第7(B)圖中的箭頭所示般，將樣品S朝長度方向拉 伸。如此一來，可以獲得於切痕C的部分，只有最內層 11完全破斷，其他層不破斷之狀態者。因此，藉由將其設 -23- 200927083 置於拉伸試驗機，如第7 ( A )圖般，可以測定最內層1 1 與中間層1 2間的界面的剝離強度。 (3 )透明性 依據JIS K 7136來測定高壓蒸汽滅菌前後的霧度。 (Ο耐熱性 q 以噴灑式高壓蒸汽滅菌機將載置於開有圓孔的衝壓金 屬托盤上的醫療容器予以高壓蒸汽滅菌，以目視來評估醫 療容器的外觀。 〇：滅菌後，無變形或收縮。 △:表面粗糙等，有少許的變形收縮。 X:變形或收縮大，有圓孔狀的托盤痕跡等》 (5)成形穩定性 Q 評估充氣成形中的管形狀薄膜的形狀穩定性及薄膜的 縐折產生狀況。 〇：管形狀一定。薄膜見不到縐褶。 X:管形狀不穩定，管徑有偏差。薄膜部分見到縐 [實施例2] 於實施例1中，除了改變最外層的組成與埠口部22 的構成以外，其餘設爲相同，獲得醫療容器20。 -24- 200927083 最外層係使用將190°C中之MFR爲l.lg/ΙΟ分鐘、密 度0.92 7 g/cm3之高壓法低密度聚乙烯「NOVATEC (日本 聚乙烯株式會社製）」；及190°C中之MFR爲3.5g/10分 鐘、密度0.956 g/cm3之高密度聚乙烯「NOVATEC (曰本 聚乙烯株式會社製）」以7 : 3質量比予以混合者。 埠口部22係將由藉由射出成形所製造的環狀聚烯烴 所形成的圓筒構件，以設定爲250 °C的預熱模具予以加 熱，插入由第2圖的吹製成形體所形成的收容部21的埠 口部22側，以220 °C予以熱密封並予以裝著後所構成。另 外，塡充水100mL後，將橡膠栓裝塡於圓筒構件，之後， 進而將環狀的蓋構件按壓於橡膠栓的周緣部而配置，將圓 筒構件與蓋構件予以超音波熔接。另外，圓筒構件與蓋構 件係使用COP1。而且，與實施例1同樣地評估。將結果 表示於表中。 Q [實施例3] 於最內層的形成上，只是使用COP2以外，與實施例 1同樣爲之，獲得醫療容器20，同樣地評估。將結果表示 於表中。 另外，在本實施例中，作爲橡膠栓體22a，係使用於 橡膠栓的外周部以射出成形法設置有由中間層所使用的 LLDPE所形成之層者。 [實施例4] -25- 200927083 於中間層的形成上，只是使用190°C中之MFR爲 3.5g/10分鐘、密度〇·918 g/Cm3之單一活化部位系LLDPE 「HARMOREX (日本聚乙烯株式會社製）」來形成以外， 與實施例3相同，獲得醫療容器20 ’同樣地評估。將結果 表示於表中。 另外，在本實施例中’作爲橡膠栓體22a，係使用於 橡膠栓的外周部以射出成形法設置有由中間層所使用的 LLDPE所形成之層者。 [實施例5] 於中間層的形成上，只是使用190°C中之MFR爲 4.0g/10分鐘、密度0.931 g/cm3之單一活化部位系LLDPE 「YUMERIT (宇部興產股份有限公司製）」以外，與實施 例3相同，獲得醫療容器20，同樣地評估。將其結果表示 於表中。 φ 另外，在本實施例中，作爲橡膠栓體22a，係使用於 橡膠栓的外周部以射出成形法設置有由中間層所使用的 LLDPE所形成之層者。 [實施例6] 於中間層的形成上，使用將 190°C中之 MFR爲 2.0g/10分鐘、密度0.904 g/cm3之單一活化部位系LLDPE 「YUMERIT0520F (宇部興產股份有限公司製）」：及 190°C 中之 MFR 爲 3.5g/l〇 分鐘、密度 0.956 g/cm3 之 -26- 200927083 HDPE「NOVATEC (日本聚乙烯株式會社製）」以 8:2 的質量比予以混合者以外，與實施例1相同，獲得醫療容 器20，同樣地評估。將其結果表示於表中。 另外，在本實施例中，作爲橡膠栓體22a，係使用於 橡膠栓的外周部以射出成形法設置有由COP 1所形成之層 者0 [實施例7] 如下述般製造塡充有1〇〇 ml之水的第3圖之醫療容 器30。 首先，藉由使用多層充氣薄膜成形機之多層充氣法， 來製造厚度的最內層、及厚度220//m的中間層、 及厚度20/zm的最外層依序被層積的3層所形成的充氣薄 膜。 接著，將此充氣薄膜予以切斷所獲得之薄膜片藉由設 定成300 °C之加熱器以輻射加熱使其軟化，使用常溫的模 具，以真空成形機予以成形，獲得第4圖的薄膜成形品 10, ° 然後，將此薄膜成形品10’使凹部彼此相向之方式予 以2片疊合，將周緣部予以熱密封，之後，將環狀聚烯烴 的射出成形品之圓筒構件予以熱密封，形成埠口部32。 接著，從埠口部32對收容部31內塡充水1〇〇 ml 後，如第3(B)圖所示般，將橡膠栓3 2b裝塡於圓筒構 件，之後，進而將環狀的蓋構件32c按壓於橡膠栓32b的 -27- 200927083 周緣部而配置，將圓筒構件與蓋構件32c予以超音波熔 接。另外，圓筒構件與蓋構件32c係使用COP 1。 另外，最內層、中間層、最外層，都是使用與實施例 1相同的樹脂。 然後，針對已密封的醫療容器3 0進行評估。將其結 果表示於表中。 [實施例8] 如下述般製造塡充有100 ml之水的第5圖之醫療容 器40。 首先，與實施例7相同，製造3層構造的充氣薄膜。 接著，將此充氣薄膜的兩端部予以熱密封做成袋狀， 而且，於其一端熱密封COP2的射出成形品之圓筒構件， 於薄膜袋型的收容部4 1形成埠口部42。 接著，從璋口部42對收容部41內塡充水100 ml 後，將橡膠栓4 2b裝塡於圓筒構件，之後，進而將環狀的 蓋構件42b按壓於橡膠栓42a的周緣部而配置，將圓筒構 件與蓋構件42b予以超音波熔接。另外，圓筒構件與蓋構 件42b係使用COP 1。 然後，針對已密封的醫療容器40進行評估。將其結 果表示於表中。 [實施例9] 除了最外層係使用將190°C中之MFR爲lg/ΙΟ分鐘、 -28- 200927083 密度0.92 7 g/cm3之高壓法低密度聚乙烯「N0VATEC (日 本聚乙烯株式會社製）」；及190°c中之MFR爲3.5g/10 分鐘、密度0.956 g/cm3之高密度聚乙烯「NOVATEC (日 本聚乙烯株式會社製）」以7 : 3的質量比予以混合者以 外’與實施例8相同，獲得醫療容器20，同樣地進行評 估。將其結果表示於表中。 [實施例10] 除了最外層係使用將190°C中之MFR爲2.0g/10分 鐘、密度0.936 g/cm3之使用戚格勒（Ziegler)觸媒所製 造的直鏈型低密度聚乙烯「NOVATEC (日本聚乙烯株式 會社製）」：及190°C中之MFR爲3.5g/10分鐘、密度 0.95 6 g/cm3之高密度聚乙烯「NOVATEC (日本聚乙烯株 式會社製）」以7 : 3的質量比予以混合者以外，與實施 例8相同，獲得醫療容器20，同樣地進行評估。將其結果 表示於表中。 [比較例1] 實施例1中，作爲中間層的主成分，代替單一活化部 位系LLDPE，使用190°C中之MFR爲l.lg/ΙΟ分鐘、密度 0.906 g/cm3之使用戚格勒（Ziegler )觸媒所製造的 LLDPE (日本聚乙烯株式會社製）以外，與實施例1相 同，實施醫療容器的成形與評估。將評估結果表示於表 中〇 -29- 200927083 [比較例2] 於中間層的形成上，只是使用190。(：中之MFR爲 2.〇g/10分鐘、密度0.920 g/cm3之使用戚格勒（Ziegler) 觸媒所製造的LLDPE 「MOATEC (株式會社PRIME POLYMER製）以外，與實施例1相同，實施醫療容器的 成形與評估。將評估結果表示於表中。 ❹ [比較例3] 不形成最外層，做成最內層與中間層之<2層構造以 外’與實施例1相同，實施醫療容器的成形與評估。將評 估結果表示於表中。 [比較例4] 於最外層的形成上，代替HDPE，只是使用1 90°C中 Q 之MFR爲2.0g/l〇分鐘、密度0.920 g/cm3之使用戚格勒 (Ziegler )觸媒所製造的LLDPE 「MO ATEC (株式會社 PRIME POLYMER製）以外，與實施例1相同，實施醫療 容器的成形與評估。將評估結果表示於表中。 [比較例5]200927083 The medical office container 50 of Fig. 6 is provided with a partition sealing portion 52' accommodating portion 5 as a first accommodating portion 51a and a second accommodating portion 51b along the width direction of the pocket portion 51. When the user of the partition sealing portion medical chamber 50 is used, the user peels off from the external S housing portion 51a or the second housing portion 51b, and the chemical solution in the first 51a and the liquid in the second housing portion 51b are separated. The method of forming the partition wall sealing portion 52 is not limited. For example, when the portion 51 is formed, when it is heat-sealed, it may be formed by heat sealing. Further, in addition to the heat sealing, it may be carried out separately by a known sealing method such as sealing. Further, when the accommodating portion 51 is manufactured by blow molding, the mold for forming the partition sealing portion 52 is formed in the mold used in the noisy manner, and the partition sealing portion 52 can be formed. Further, although not shown, in the medical container of the present invention, the side portion, particularly the outer side of the accommodating portion, may be provided with a light shielding layer as needed. The material suitable for the light-shielding layer may, for example, be an aluminum case foil, an aluminum steamer blade film, a metal foil or a synthetic resin film, or a synthetic resin film containing a pigment. Among these light-shielding layers, the vapor-deposited film, etc., not only has a light-shielding property, but also has moisture resistance, water absorption resistance, etc. 'It is more suitable from the viewpoint of improving the long-term protection of the liquid medicine contained in the medical container. . Alternatively, the light-shielding layer may be peeled off from the medical container, and the medical solution may be visually observed when used in a medical container. In the above, the storage of the medicine contained in the medical container of the present invention is divided into 52 by the first accommodating portion ► at the same time as the accommodating portion, and the pulse can be formed into a shape to facilitate the use of a gold film or an aluminum foil for the external medicinal solution. Or sexual and non-existent settings are from the outside, taking the medicine -20-200927083 liquid as an example to illustrate 'but 'not only the liquid medicine' may also be a medicine formed by a powder such as an antibiotic substance. Further, the "specific chemical solution" may be a chemical solution used as an injection agent such as physiological saline, a circulator system drug, a contrast agent, and an antibacterial agent. But ' is not limited to these. [Examples] Hereinafter, the present invention will be specifically described by way of Examples. However, the present invention is not limited to the following examples. [Example 1] A medical container 20 of Fig. 2, which was filled with 100 ml of water, was produced as follows. First, by the multi-layer blow molding method using a multi-layer blow molding machine, the innermost thickness was integrally formed. The layer, the intermediate layer having a thickness of 250/zm, and the outermost layer having a thickness of 20/m is a accommodating portion 21 and a mouth portion 22 which are formed by blowing a three-layer structure which is sequentially laminated. Next, the inside of the accommodating portion 21 is filled with water 100 ml from the mouth portion 22, and then the rubber plug 22a is heat-sealed to the mouth portion 22 to seal the medical container 20. The rubber plug body 22a is provided on the outer peripheral portion of the rubber plug by an injection molding method. The melting flow rate in 280 ° C according to ISO 1133 (hereinafter referred to as [MFR]. Further, examples and comparative examples) In the case of the MFR measurement, the total load is 21.18 N.) The cyclic polyolefin "ZEONEX (manufactured by Sakamoto Co., Ltd.)" of 17 g/10 min and a glass transition temperature of 136 ° C (hereinafter referred to as "COP1") "." The layer formed. -21 - 200927083 In addition, the innermost layer is a cyclic polyolefin "ZEONOA (Japan Japan) which uses COP 1 and according to ISO 1133, MFR of 280 °C is 20g/10 minutes, and glass transition temperature is 102 °C. (manufactured by the company) (hereinafter referred to as "COP2") A mixture of cyclic polyolefins mixed at a mass ratio of 1:1. The Tg of this mixed cyclic polyolefin was only observed to be U9 °C. The intermediate layer is a LLDPE (hereinafter, also referred to as a single activation site system LLDPE) which is produced by a single activation site catalyst, and has an MFR of lg/ΙΟ minutes and a density of 0.906 g/cm 3 at 190 °C. HDPE "HARMOREX (made by Nippon Polyethylene Co., Ltd.)": HDPE "NOVATEC (made by Nippon Polyethylene Co., Ltd.)" having an MFR of 3.5 g/10 min and a density of 0.956 g/cm3 at 190 °C is 8:2 The mass ratio is mixed. The outermost layer was HDPE "NO VATEC (Japan Polyethylene Co., Ltd.)" having an MFR of 190 ° C of 3.5 g / l 0 min and a density of 0.95 5 g / cm 3 . The medical container 20 of FIG. 2 thus obtained and filled with water was subjected to autoclaving at 121 ° C for 30 minutes by spray-type autoclaving, and the characteristics before and after the evaluation were evaluated as follows. In the table. Further, in the examples and the comparative examples, the evaluation of the barrier property and the forming stability was carried out only in the case of forming a film and forming an accommodating portion, and as in the case of Example 1, it was formed by multi-layer blow molding. In the case of the accommodating department, no evaluation is made. -22- 200927083 (Evaluation method) (〇Resistance resistance Two layers of lOcmxlOcm are laminated in such a manner that their outermost layers are joined to each other, and a load of 98 N/100 cm 2 is applied thereto to maintain 601: After 24 hours, it was cooled to room temperature, and after removing the load, two sheets of the film were peeled off. The peeling state at this time was evaluated in the following two stages. 〇: easy peeling X: resistance at peeling (2) Peeling strength A rectangular sample S having a width of 15 mm was cut out from the medical container before and after autoclaving, and is schematically shown in Fig. 7 (A), and the innermost layer 11 and the intermediate layer were measured at a tensile speed of 300 mm/min. The T-peel strength of 12 according to JIS K68 54-3. The test was carried out by a tensile tester. The symbol P in the figure indicates the chuck of the tensile tester. In addition, as shown in Figure 7 (A) As shown in the figure, the sample S is formed such that only the innermost layer 11 is broken at the breaking portion V, first, as shown in the plan view of Fig. 7(B), cut out by the medical container. Both ends of the sample S in the width direction are provided with a cut C at two places facing each other, as in the seventh ( B) The sample S is stretched in the longitudinal direction as indicated by the arrow in the figure. In this way, the portion of the cut C can be obtained, and only the innermost layer 11 is completely broken, and the other layers are not broken. By placing the -23-200927083 in a tensile tester, as shown in Fig. 7 (A), the peel strength at the interface between the innermost layer 1 1 and the intermediate layer 12 can be measured. (3) Transparency The haze before and after autoclaving was measured according to JIS K 7136. (ΟHeat resistance q The medical container placed on the punched metal tray with round holes was autoclaved by a spray-type autoclave to visually observe Evaluate the appearance of the medical container. 〇: After sterilization, there is no deformation or shrinkage. △: The surface is rough, etc., with a slight deformation and contraction. X: Large deformation or shrinkage, and there are round-hole tray marks, etc. (5) Forming stability Q. The shape stability of the tube-shaped film during inflation molding and the occurrence of film collapse were evaluated. 〇: The tube shape was constant. The film did not see creases. X: The tube shape was unstable and the tube diameter was deviated.绉 [Embodiment 2] In Embodiment 1, The composition of the outermost layer and the composition of the mouth portion 22 were changed, and the rest were set to be the same, and the medical container 20 was obtained. -24- 200927083 The outermost layer used MFR at 190 ° C was l.lg / min, density 0.92 High-pressure method low-density polyethylene of 7 g/cm3 "NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)"; and high-density polyethylene having a MFR of 3.5 g/10 min and a density of 0.956 g/cm3 at 190 ° C "NOVATEC ( "Sakamoto Polyethylene Co., Ltd.)" was mixed at a mass ratio of 7:3. The mouth portion 22 is a cylindrical member formed of a cyclic polyolefin produced by injection molding, heated by a preheating mold set at 250 ° C, and inserted into a blow molded body formed in Fig. 2 The side of the mouth portion 22 of the accommodating portion 21 is heat sealed at 220 ° C and attached. Further, after filling 100 mL of water, the rubber plug was attached to the cylindrical member, and then the annular cover member was pressed against the peripheral edge portion of the rubber plug, and the cylindrical member and the cover member were ultrasonically welded. Further, COP1 is used for the cylindrical member and the cover member. Further, it was evaluated in the same manner as in Example 1. The results are shown in the table. [Example 3] A medical container 20 was obtained in the same manner as in Example 1 except that COP2 was used for the formation of the innermost layer, and the evaluation was performed in the same manner. The results are shown in the table. Further, in the present embodiment, the rubber plug body 22a is used for the layer formed of the LLDPE used in the intermediate layer by the injection molding method in the outer peripheral portion of the rubber plug. [Example 4] -25- 200927083 In the formation of the intermediate layer, only a single activation site of LLDPE "HARMOREX (Japan Polyethylene) having a MFR of 3.5 g/10 min at 190 ° C and a density of 918 918 g/cm 3 was used. In the same manner as in the third embodiment, the medical container 20' was evaluated in the same manner as in the case of the formation of the product. The results are shown in the table. Further, in the present embodiment, the rubber plug body 22a is used for the outer peripheral portion of the rubber plug to be provided with a layer formed of LLDPE used for the intermediate layer by injection molding. [Example 5] In the formation of the intermediate layer, a single activation site of LLDPE "YUMERIT (manufactured by Ube Industries, Ltd.)" having a MFR of 4.0 g/10 min and a density of 0.931 g/cm3 at 190 ° C was used. The medical container 20 was obtained in the same manner as in Example 3 except that it was evaluated in the same manner. The results are shown in the table. Further, in the present embodiment, the rubber plug body 22a is used in the outer peripheral portion of the rubber plug to form a layer formed of LLDPE used in the intermediate layer by injection molding. [Example 6] A single activation site of LLDPE "YUMERIT0520F (manufactured by Ube Industries, Ltd.)" having a MFR of 190 ° C of 2.0 g/10 min and a density of 0.904 g/cm 3 was used for the formation of the intermediate layer. : -26-200927083 HDPE "NOVATEC (made by Nippon Polyethylene Co., Ltd.)" with an MFR of 3,000 °C and a density of 0.956 g/cm3 at 190 °C, which is mixed with a mass ratio of 8:2. The medical container 20 was obtained in the same manner as in Example 1, and was evaluated in the same manner. The results are shown in the table. Further, in the present embodiment, the rubber plug body 22a is used in the outer peripheral portion of the rubber plug, and the layer formed by the COP 1 is provided by the injection molding method. [Example 7] It is manufactured as follows. The medical container 30 of Fig. 3 of the water of ml. First, the innermost layer of the thickness, the intermediate layer having a thickness of 220/m, and the outermost layer having a thickness of 20/zm are sequentially laminated by using a multilayer inflation method of a multi-layered air-filled film forming machine. Formed aerated film. Then, the film sheet obtained by cutting the gas-filled film was softened by radiant heating by a heater set at 300 ° C, and molded by a vacuum forming machine using a mold at room temperature to obtain a film formation of FIG. Then, the film molded article 10' is laminated in such a manner that the concave portions face each other, and the peripheral portion is heat-sealed, and then the cylindrical member of the injection molded article of the cyclic polyolefin is heat-sealed. The mouth portion 32 is formed. Next, after the inside of the accommodating portion 31 is filled with water from the mouth portion 32, the rubber plug 3 2b is attached to the cylindrical member as shown in the third figure (B), and then the ring is further formed. The lid member 32c is pressed against the peripheral portion of the rubber plug 32b from -27 to 200927083, and the cylindrical member and the lid member 32c are ultrasonically welded. Further, COP 1 is used for the cylindrical member and the lid member 32c. Further, the same resin as in Example 1 was used for the innermost layer, the intermediate layer, and the outermost layer. Then, an evaluation is made for the sealed medical container 30. The results are shown in the table. [Example 8] A medical container 40 of Fig. 5 filled with 100 ml of water was produced as follows. First, in the same manner as in Example 7, an air-filled film having a three-layer structure was produced. Then, both end portions of the gas-filled film are heat-sealed to form a bag shape, and a cylindrical member of the injection molded article of COP 2 is heat-sealed at one end thereof, and a mouth portion 42 is formed in the film bag-type accommodating portion 41. Then, after the inside of the accommodating portion 41 is filled with water 100 ml from the mouth portion 42, the rubber stopper 4 2b is attached to the cylindrical member, and then the annular cover member 42b is pressed against the peripheral edge portion of the rubber stopper 42a. In the arrangement, the cylindrical member and the cover member 42b are ultrasonically welded. Further, COP 1 is used for the cylindrical member and the lid member 42b. Evaluation is then performed on the sealed medical container 40. The results are shown in the table. [Example 9] A high-pressure method low-density polyethylene "N0VATEC (made by Nippon Polyethylene Co., Ltd.) having an MFR of lg / ΙΟ minute, -28 - 200927083 density of 0.92 7 g / cm 3 at 190 ° C was used for the outermost layer. And a high-density polyethylene having a MFR of 3.5 g/10 min at 190 ° C and a density of 0.956 g/cm 3 "NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)" is mixed with a mass ratio of 7:3. In the same manner as in Example 8, the medical container 20 was obtained and evaluated in the same manner. The results are shown in the table. [Example 10] In addition to the outermost layer, a linear low-density polyethylene produced by using a Ziegler catalyst having an MFR of 190 ° C of 2.0 g/10 min and a density of 0.936 g/cm 3 was used. NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.): a high-density polyethylene having a MFR of 3.5 g/10 min at 190 ° C and a density of 0.95 6 g/cm 3 "NOVATEC (manufactured by Nippon Polyethylene Co., Ltd.)" 7 : The medical container 20 was obtained in the same manner as in Example 8 except that the mass ratio of 3 was mixed, and the evaluation was performed in the same manner. The results are shown in the table. [Comparative Example 1] In the first embodiment, as the main component of the intermediate layer, in place of the single activation site system LLDPE, the use of the MFR at 190 ° C was 1.lg / ΙΟ minute, and the density of 0.906 g / cm 3 was used. In the same manner as in Example 1, except for LLDPE (manufactured by Nippon Polyethylene Co., Ltd.) manufactured by a catalyst, the formation and evaluation of a medical container were carried out. The evaluation results are shown in the table 〇 -29- 200927083 [Comparative Example 2] On the formation of the intermediate layer, only 190 was used. (In the same manner as in the first embodiment, the MFR is 2. 〇g/10 minutes, and the density is 0.920 g/cm3, which is the same as in the first embodiment except that the LLDPE manufactured by Ziegler Catalyst is "MOATEC (manufactured by PRIME POLYMER Co., Ltd.). The measurement and evaluation of the medical container were carried out. The evaluation results are shown in the table. [Comparative Example 3] The outermost layer and the intermediate layer were formed without the outermost layer, and the same as in the first embodiment. Forming and evaluation of medical containers. The results of the evaluation are shown in the table. [Comparative Example 4] In the formation of the outermost layer, instead of HDPE, the MFR of Q at 1 90 ° C was 2.0 g/l 〇 minutes, density 0.920. In the same manner as in the first embodiment, the formation and evaluation of the medical container were carried out in the same manner as in the first embodiment except for the use of the LLDPE manufactured by the Ziegler catalyst (manufactured by PRIME POLYMER Co., Ltd.). [Comparative Example 5]
於最外層的形成上，代替HDPE，1 90。(：中之MFR爲 2.0 g/10分鐘、密度0.920 g/cm3之使用戚格勒（Ziegler) 觸媒所製造的 LLDPE 「MOATEC (株式會社 PRIME -30- 200927083 POLYMER製）以外，與實施例8相同，實施醫療容器的 成形與評估。將評估結果表示於表中。In the formation of the outermost layer, instead of HDPE, 1 90. (In the case of the MFR of 2.0 g/10 min and the density of 0.920 g/cm3, the LLDPE manufactured by Ziegler Catalyst, "MOATEC (manufactured by PRIME -30-200927083 POLYMER)), and Example 8 In the same manner, the formation and evaluation of the medical container were carried out. The evaluation results are shown in the table.
-31 - 200927083-31 - 200927083
實施例10 薄膜 〇 CN fS oo 〇 〇 實施例9 薄膜 〇 oo CN 〇 〇 實施例8 薄膜 〇 CS SO CM o 寸 〇 X 實施例7 真空成形 1 … CM m (N (N 〇 X 實施例6 吹製 1 (N cs (N 〇 1 實施例5 吹製 1 <N o *>〇 〇 1 實施例4 吹製 1 rj On (N 〇 1 實施例3 吹製 1 Ό CN CN (N m Δ有輕微 托盤痕跡 1 實施例2 吹製 1 in (N (N (N cs 〇 1 實施例1 吹製 1 (N so cs (N 〇 1 成形法 耐阻隔性 高壓滅菌前 高壓滅菌後 高壓滅菌前 高壓滅菌後 耐熱性 成形穩定性 剝離強度 [N/15mm 1 透明性 [%] -32- 200927083 [表2] 比較例1 比較例2 比較例3 比較例4 比較例5 成形法 吹製 吹製 吹製 吹製 薄膜 耐阴 L隔性 一 — — — X 剝離強度 [N/15mm] 高壓滅菌前 25 20 25 26 26 高壓滅菌後 10 5 25 26 26 透明性 [%] 高壓滅菌前 34 38 22 23 8 高壓滅菌後 42 50 變形大 無法測量 變形大 無法測量 變形大 無法測量 耐熱性 〇 〇 △擁微 托盤痕跡 X X 成形穩定性 一 一 — 一 〇 在作爲中間層的主成分，使用單一活化部位系 LLDPE -且倂用HDPE的實施例1〜3及6〜10中，可以 獲得藉由高壓蒸汽滅菌之剝離強度或透明性的降低受到抑 制，耐熱性也優異的醫療容器。另一方面，在將戚格勒系 LLDPE與HDPE倂用的比較例1中所獲得的醫療容器，藉 由高壓蒸汽滅菌之剝離強度或透明性的降低很大。比較中 間層只是使用單一活化部位系LLDPE之實施例3及5與 只是使用戚格勒系LLDPE的比較例2，也見到同樣的傾 向。 在不設置最外層的比較例3中，藉由高壓蒸汽滅菌之 透明性的降低很大，且耐熱性也差。最外層不含有HDPE 之比較例4及5，也見到與比較例3同樣的傾向。作爲最 外層的成分，於HDPE倂用高壓法低密度聚乙烯之實施例 9及1〇中，與最外層只是HDPE之實施例7或8比較，成 形穩定性更爲優異。 -33- 200927083 進而’於實施例8中’薄膜的耐阻隔性雖然良好，但 是，在比較例5中，係屬不良。 [產業上之利用可能性] 如依據本發明，可以提供：不使用接著劑，由環狀聚 烯烴所形成的最內層與其他層可以良好地接著，耐熱性也 優異，於薄膜的情形時，耐阻隔性也良好的醫療容器用多 層體；及由此醫療容器多層體所形成，即使以高壓蒸汽等 來滅菌，透明性或剝離強度等之特性劣化也少的醫療容 器。因此，本發明在產業上有用。 【圖式簡單說明】 第1圖係本發明之多層體的一例之剖面圖。 第2(A)圖係表示本發明之醫療容器的一例之平面 圖，（B )係沿著（A )之I一 Γ線的剖面圖。 第3(A)圖係表示本發明之醫療容器的其他一例的 平面圖。（B)係表示埠口部的其他一例之平面圖。 第4(A)圖係製造第3圖的醫療容器時所使用的薄 膜成形品的正面圖，（B )爲其側面圖。 第5圖係表示本發明之醫療容器的進而其他一例的平 面圖。 第6圖係表示本發明之醫療容器的一例之複室醫療容 器的平面圖。 第7(A)圖係說明實施例的剝離試驗之模逛圖 -34- 200927083Example 10 Film 〇CN fS oo 〇〇Example 9 Film 〇oo CN 〇〇Example 8 Film 〇CS SO CM o 〇X Example 7 Vacuum Forming 1 ... CM m (N (N 〇X Example 6 Blowing) 1 (N cs (N 〇 1 Example 5 blowing 1 <N o *> 〇〇 1 Example 4 blowing 1 rj On (N 〇 1 Example 3 blowing 1 Ό CN CN (N m Δ There are slight tray marks 1 Example 2 Blowing 1 in (N (N (N cs 〇1) Example 1 Blowing 1 (N so cs (N c1 forming method for high-pressure sterilization before autoclaving before high-pressure sterilization) After heat sterilization, heat-resistant forming stability peeling strength [N/15 mm 1 transparency [%] -32- 200927083 [Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Blown blowing by forming method Blowing film resistant to negative L-slip one — — — X Peeling strength [N/15mm] Before autoclaving 25 20 25 26 26 After autoclaving 10 5 25 26 26 Transparency [%] Before autoclaving 34 38 22 23 8 High pressure After sterilization, 42 50 deformation is too large to measure large deformation, large deformation cannot be measured, and heat resistance cannot be measured. Tray trace XX Forming stability - one of the main components of the intermediate layer, using a single activation site LLDPE - and using HDPE in Examples 1 to 3 and 6 to 10, can be obtained by autoclaving A medical container which is excellent in heat resistance and is excellent in peeling strength and transparency. On the other hand, the medical container obtained in Comparative Example 1 in which 戚格勒 LLDPE and HDPE are used is sterilized by autoclaving. The peel strength or the decrease in transparency was large. The comparison of the intermediate layer was carried out only in Examples 3 and 5 using a single activation site LLDPE and Comparative Example 2 using only the Zigler LLDPE, and the same tendency was observed. In Comparative Example 3 of the outer layer, the reduction in transparency by autoclaving was large and the heat resistance was also inferior. In Comparative Examples 4 and 5 in which the outermost layer did not contain HDPE, the same tendency as in Comparative Example 3 was also observed. The outermost layer of the composition, in Examples 9 and 1 of the HDPE® high-pressure process low-density polyethylene, is more excellent in forming stability than the embodiment 7 or 8 in which the outermost layer is only HDPE. -33- 200927083 'In Example 8' resistance although good barrier films, however, in Comparative Example 5, the Department is poor. [Industrial Applicability] According to the present invention, it is possible to provide that the innermost layer and the other layer formed of the cyclic polyolefin can be satisfactorily adhered without using an adhesive, and the heat resistance is also excellent, in the case of a film. A multilayer container for a medical container which is excellent in barrier properties, and a medical container formed of a multilayered body of a medical container, which is sterilized by high-pressure steam or the like, and which has little deterioration in characteristics such as transparency and peel strength. Therefore, the present invention is industrially useful. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a multilayer body of the present invention. Fig. 2(A) is a plan view showing an example of the medical container of the present invention, and Fig. 2(B) is a cross-sectional view taken along line I of (A). Fig. 3(A) is a plan view showing another example of the medical container of the present invention. (B) is a plan view showing another example of the mouth part. Fig. 4(A) is a front view showing a film molded article used in the production of the medical container of Fig. 3, and Fig. 4(B) is a side view thereof. Fig. 5 is a plan view showing still another example of the medical container of the present invention. Fig. 6 is a plan view showing a medical treatment container of an example of the medical container of the present invention. Fig. 7(A) is a view showing the peeling test of the embodiment -34-200927083
(B )係說明（A )所使用之樣品的製作法之平面圖。 【主要元件符號說明】 1 0 :多層體，1 1 :最內層，12 :中間層，1 3 ··最外 層，20、30、40:醫療容器，50:複室醫療容器 -35-(B) is a plan view showing the method of producing the sample used in (A). [Description of main component symbols] 1 0 : Multi-layer body, 1 1 : Innermost layer, 12: Intermediate layer, 1 3 · · Outer layer, 20, 30, 40: Medical container, 50: Rehabilitation medical container -35-