CN1128005A - 防污染密封膜及其制品 - Google Patents
防污染密封膜及其制品 Download PDFInfo
- Publication number
- CN1128005A CN1128005A CN95190371A CN95190371A CN1128005A CN 1128005 A CN1128005 A CN 1128005A CN 95190371 A CN95190371 A CN 95190371A CN 95190371 A CN95190371 A CN 95190371A CN 1128005 A CN1128005 A CN 1128005A
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- China
- Prior art keywords
- layer
- film
- polyethylene
- proof sealant
- contamination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Images
Classifications
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Abstract
主要用于医疗领域的防污染密封膜,它至少具有由选自线形低密度聚乙烯、低密度聚乙烯、聚内烯、聚丁烯-1中的至少一种树脂组成的作为最内层的第1层以及通过由无定形聚烯烃、粘合性聚烯烃或乙烯-乙酸乙烯酯共聚物组成的作为粘合剂层的第2层在第1层的外侧层合的由乙烯-乙烯醇共聚物组成的第3层,利用构成第3层的乙烯-乙烯醇共聚物的阻挡作用,能够防止污染物质从第3层的外侧向第1层(最内层)侧转移。
Description
技术领域
本发明涉及防污染密封膜,尤其是可用作医疗容器用薄膜、医疗容器的包装用薄膜和医疗容器的包封用薄膜的最内层构成材料的防污染密封膜。
背景技术
作为适用于医疗容器用、医疗容器的包装用、医疗容器的包封用等用途的塑料薄膜材料,以往从防止药剂劣化和容器破损以及得到透视性等观点出发,一般使用耐气体透过性、耐透湿性、耐热性、耐冲击性、透明性优良的单层或多层薄膜。这种薄膜材料含有作为构成要素的基体材料薄膜,作为这种基体材料薄膜的树脂原料,例如可举出尼龙、聚对苯二甲酸乙二醇酯、聚乙烯醇等。
另外,以往以提高热封性为目的,使用硅系、环氧系、氨基甲酸酯系、氨基甲酸酯-环氧系、丙烯酸系等粘合剂,将密封膜层合在上述薄膜材料的基材薄膜上。在此情况中,作为密封膜,主要使用由低密度聚乙烯那样的低熔点和低密度树脂组成的薄膜。这种树脂薄膜具有高的热封强度,能低温密封,而且即使附着尘埃等也能得到规定的热封强度,具有作为密封薄膜的优良品质和性能。
在具备基材薄膜、粘合剂层和密封膜的上述薄膜材料中,基材薄膜和粘合剂往往含有污染物质。
污染物质和污染原因列举如下。
(1)在基材薄膜成形时,为了提高该薄膜的各种性质,在成形材料中添加的各种添加剂。
添加剂:邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二正丁酯(DNBP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二乙基己酯(DEHP)等邻苯二甲酸酯,氯化石蜡、己二酸酯、脂肪酰胺、磷系抗氧化剂、酚系抗氧化剂等。
(2)在挤出成形机的模头上往往涂敷防锈剂、脱模剂(例如硅油)。这种防锈剂、脱模剂在基材薄膜成形时附着在该薄膜上,污染薄膜。
(3)由上述污染物质或含有所述污染物质的水附着在基材薄膜外面引起的污染。
(4)在基材薄膜含有尼龙树脂的情况下,作为尼龙树脂成分含有的己二酸、己内酰胺。
(5)包含在上述粘合剂中的反应生成物。
在过去提供的上述薄膜材料中,构成最内层的密封膜对上述污染物质没有阻挡性,因此如果基材薄膜和/或粘合剂含有上述污染物质,则污染物质透过粘合剂层和密封膜转移到最内层的内侧。
因此,在由这种薄膜材料构成的医疗容器、医疗容器的包装袋、医疗容器的包封等各种制品中,不能使内容物(例如药剂)免受污染物质引起的污染。
另外,如果药剂被污染物质污染,则有产生药剂的分解或外观上的变化或劣化等问题的危险。
发明的公开
本发明的一个目的在于提供具有优良的热封性、并对上述污染物质具有阻挡性的防污染密封膜。
本发明的另一个目的在于提供包含上述密封膜作为最内层的防污染的医疗容器用薄膜、医疗容器的包装用薄膜和医疗容器的包封用薄膜。
本发明的又一个目的在于提供包含上述密封膜作为最内层的防污染的各种制品,例如医疗容器、医疗容器的包装袋(以下称为“包装袋”)和医疗容器的包封(以下称为“包封”)。
本发明的其他特征由以下描述说明。
本发明提供了防污染密封膜,它是以选自线形低密度聚乙烯、低密度聚乙烯、聚丙烯、聚丁烯-1中的至少一种树脂组成的第1层作为最内层的多层密封膜,其特征是通过由无定形聚烯烃、粘合性聚烯烃或乙烯-乙酸乙烯酯共聚物组成的作为粘合层的第2层,在第1层的外侧层合由乙烯-乙烯醇共聚物组成的第3层。
除了上述1-3层的3层结构外,本发明的防污染密封膜也可以在构成其最外层的第3层的外测依次层合第4层和第5层。
此时,使用在第2层中所述的树脂形成第4层,使用在第1层中所述的树脂形成第5层。
本发明的密封膜适用于形成医疗容器用薄膜、医疗容器的包装用薄膜、医疗容器的包封用薄膜的最内层。
在此,所谓医疗容器用薄膜是指用于医疗容器成形的薄膜。
另外,所谓医疗容器的包装用薄膜是指将医疗容器整体包在内部、密封的包装袋的成形中使用的薄膜(以下,称为“包装用薄膜”)。
此外,所谓医疗容器的包封用薄膜是指将医疗容器的至少一个室包封、通过与该容器部分粘合形成密封的包封的成形中使用的薄膜(以下称为“包封用薄膜”)。
附图的简要说明
图1是表示3层型的本发明防污染密封膜的剖面图。
图2是表示5层型的本发明防污染密封膜的剖面图。
图3是表示由包含本发明防污染密封膜的薄膜成形的医疗容器的一例的纵剖面图。
图4是表示由与图3相同的薄膜成形的包装袋的一例的纵剖面图。
图5是表示由与图3相同的薄膜成形的包装袋的另一例的纵剖面图。
图6是表示由与图3相同的薄膜成形的包封的一例的纵剖面图。
图7是表示本发明的防污染密封膜部分粘合在包装用薄膜或包封用薄膜的基材薄膜上的状态的纵剖面图。
实施发明的最佳方式
下面参照附图说明本发明的实施例。
在图1中示出3层结构的本发明的防污染密封膜的一例。
构成最内层的第1层1是热封性理想的层,由选自线形低密度聚乙烯、低密度聚乙烯、聚丙烯、聚丁烯-1中的至少一种树脂制成,其中优选线形低密度聚乙烯或低密度聚乙烯。
另外,第1层1也可以是相溶性不同的二种以上树脂的混合树脂。
再有,上述低密度适宜地表示密度为0.905-0.945g/cm3。
第1层1的厚度为10μm以上,优选在约10-40μm的范围内适当选择。
为了防止污染物质从外部向最内层(第1层)侧转移,通过第2层2在第1层1的外侧设置对污染物质有阻挡作用的第3层3。
第3层3由对污染物质有阻挡性的乙烯-乙烯醇共聚物(别名:乙烯-乙酸乙烯酯共聚物皂化物)形成,厚度为10μm以上、尤其是约10-25μm。上述树脂的乙烯共聚摩尔比可以在大范围内选择,但从柔软性、对污染物质的阻挡性等考虑,理想的是29-44%。
虽然形成第3层3的乙烯-乙烯醇共聚物可用与第1层1的共挤出的方法形成2层薄膜,但其层间粘合强度比通常的共挤出薄膜的层间粘合强度低很多,这是不令人满意的。因而按照本发明,在第3层3和第1层1(最内层)之间设置对两层的粘合性俱佳的第2层2。
第2层2由无定形聚烯烃、粘合性聚烯烃或者根据需要由粘合性改善的乙烯-乙酸乙烯酯共聚物构成,优选形成5-25μm、更优选形成5-15μm的厚度。
作为用于形成第2层2的无定形聚烯烃,可举出密度为0.880-0.890g/cm3的乙烯-α-烯烃共聚物(以下称为“无定形聚乙烯”)、或者密度为0.880-0.890g/cm3的丙烯-α-烯烃共聚物(以下称为“无定形聚丙烯”)等,其中优选无定形聚乙烯。这里,作为α-链烯,例如可举出丙烯、1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十一碳烯、1-十二碳烯等碳原子数为3-1 2的烯烃,其中优选与1-丁烯的共聚物。但是在丙烯-α-烯烃共聚物的场合该a-烯烃不包括丙烯。
另外,粘合性聚烯烃是在聚乙烯、聚丙烯等聚烯烃上接枝聚合马来酸、粘合性改善的聚烯烃,例如可举出粘合性聚乙烯、粘合性聚丙烯等,其中优选粘合性聚乙烯。
乙烯-乙酸乙烯共聚物依乙烯共聚摩尔比的不同有粘合性优良者和差者,在前者情况下,原封不动地使用,在后者情况下,将马来酸接枝聚合,改进粘合性再使用。
第1层1和第2层2在对污染物质有阻挡性的第3层3的内侧形成,所以不希望含有污染物质。因而,用于形成第1层1和第2层2的上述树脂在不添加会成为污染物质的添加剂的条件下使用。
另外,因为第3层3也不使用添加剂形成,所以也没有添加剂从第3层向内测转移。
本发明的防污染密封膜如图1所示至少具备由第1层1(最内层)、第2层2和第3层3构成的3层结构是必要的,根据需要可以在第3层3的外侧层合其他层。
此时,作为其他层,可以适当选用公知的塑性树脂层,含有污染物质没有特别问题。
为了使本发明的密封膜具有透明性和柔软性,如图2所示,理想的是,通过由无定形聚烯烃、粘合性聚烯烃或者根据需要粘合性改进的乙烯-乙酸乙烯酯共聚物组成的作为粘合剂层的第4层4层合选自线形低密度聚乙烯、低密度聚乙烯、聚丙烯、聚丁烯-1中的至少一种树脂构成的第5层5作为其他层。第4层4的厚度优选在5-25μm、更优选在5-15μm的范围内适当选择,第5层5的厚度优选在10-40μm、更优选在10-20μm的范围内适当选择。
图1型和图2型的本发明的防污染密封膜的整体厚度都在50-80μm的范围内适当选择。
本发明的多层密封膜可适当选用水冷式或空冷式共挤出吹塑法、共挤出T型模头法等制造方法来制造。
通过在本发明的密封膜的外层侧层合基材薄膜,可得到医疗容器用薄膜、包装用薄膜、包封用薄膜。
作为在基材薄膜上层合本发明的密封膜的手段,可以适当采用于式层合法、湿式层合法。另外,在本发明的密封膜的最外层具有热封性、而且基材薄膜的最内层具有热封性的场合,可以使用热封手段进行粘合。
按照常规方法,通过将上述各种薄膜成形成适宜的形态,可以分别得到的例如图3-6所示的医疗容器、包装袋及包封等各种制品。
图3表示在基材薄膜B上层合本发明的密封膜A得到的医疗容器用薄膜和由该薄膜成形的医疗容器a。作为基材薄膜B,可以使用公知的用于形成医疗容器的各种薄膜。
图4、5表示在基材薄膜B1上层合本发明的密封膜得到的包装用薄膜和由该薄膜成形的包装袋b,在包装袋b内封入医疗容器a1、a2,图5表示在折叠状态下封入的复室容器a2。
在医疗容器a1、a2内的药剂非常容易因氧和湿气变质的场合下,构成包装袋b的基材薄膜B1必须使用具有耐气体透过性和耐透湿性的薄膜以防止医疗容器a1、a2内的药剂变质。
作为具有优良的耐气体透过性和耐透湿性的基材薄膜B1,可以使用在聚烯烃薄膜上层合不透氧和水蒸汽的铝箔而得的复合膜,以及由聚对苯二甲酸乙二醇酯(PET)、聚偏氯乙烯、聚乙烯醇、聚酰胺、乙烯-乙酸乙烯酯共聚物皂化物等组成的单层或多层树脂薄膜材料,或者该树脂薄膜材料和上述复合膜的层合薄膜材料。
另外,作为其他材料,也可以适当使用聚乙烯醇薄膜、聚对苯二甲酸乙二醇酯薄膜或者在乙烯-乙酸乙烯酯共聚物皂化物薄膜上形成氧化硅蒸镀层的复合薄膜等。
作为含这种复合膜作为构成要素的多层薄膜,例如可举出如下的多层薄膜。
(I)在聚乙烯醇薄膜上形成氧化硅蒸镀层的复合膜和在该复合膜的氧化硅蒸镀层上利用干式层合法层合PET薄膜(最外层)得到的多层薄膜。
(II)在聚乙烯醇薄膜上形成氧化硅蒸镀层的复合膜和在该复合膜的氧化硅蒸镀层上利用于式层合法通过重叠上述多层薄膜(I)的聚乙烯酵薄膜面层合得到的多层薄膜。
另外,包装袋b也用于保护医疗容器a1、a2不受外部撞击,在此场合下,作为基材薄膜B1,使用含有PET、尼龙、聚乙烯、聚丙烯等具有良好的冲击强度的薄膜作为构成要素的单层或多层薄膜材料。
图6表示在基材薄膜B2上层合本发明的密封膜A形成的包封用薄膜及由该薄膜成形的包封C,该包封C包封着复室容器a2的一个室。
上述包封C以与包装袋b相同的目的使用,因而作为基材薄膜B2,使用与包装袋b的基材薄膜B1相同的耐气体透过性和耐透湿性良好的薄膜材料。
在包封用薄膜或包装用薄膜中,密封薄膜A有相对于基材薄膜B1、B2全面粘合的情况(如图4-6所示),和在与基材薄膜B1、B2之间形成空间的情况下部分粘合的情况(如图7所示)。
本说明书虽然在图1-7中示出本发明的防污染薄膜、医疗容器、包装袋和包封,但本发明丝毫不限定于这些实施形式、形状和大小等,在不脱离本发明要点的范围内,当然可以以各种形式实施本发明。
使用在本发明的密封薄膜的外层侧层合基材薄膜得到的薄膜材料成形的制品,例如图3-6所示的医疗容器、包装袋和包封,因为上述密封薄膜对污染物质具有阻挡性,所以基材薄膜中包含的污染物质和/或来自外部的污染物质不会侵入到医疗容器的内部,能够防止由污染物质引起的药剂污染。
图3-6所示的医疗容器用于包封一般的药剂,作为药剂,粉末剂、液剂、固形剂中的任一种都可以。
作为粉末剂,可以举出例如抗生素、抗癌剂、蛋白质、肽制剂、甾族化合物剂、血栓溶解剂或维生素剂等。作为抗生素,可例示出头孢唑啉、氨苄青霉素等β-内酰胺类、亚胺培南(imipenum)等1-碳青霉素烯(carbapenem)类、卡那霉素等氨基糖苷类、万古霉素等多肽类,红霉素等大环内酯类等。作为液剂,可举出例如生理盐水、葡萄糖液、注射用蒸馏水、电解质液、氨基酸液、脂肪乳剂等。
在上述药剂中,抗生素等的粉末剂,因为使用时必须溶解在生理盐水或葡萄糖液等溶剂中对患者给药,所以最近进行简化其操作的尝试,例如开发了如图6所示的二个室的复室容器。
在图6中,易受微量污染物质的不良影响的抗生素等药剂被收纳在上室,生理盐水或葡萄糖液等溶解剂被收纳在下室,仅上室用本发明的包封进行双重包装。
下面举出本发明的实施方案和比较例,接着举出使用它们的试验例。
[本发明1](图1型)
利用水冷式共挤出吹塑成形机成形三层结构的密封膜:以乙烯-乙烯醇共聚物[可乐丽(株)制造(乙烯共聚摩尔比为44%)](以下记作EVOH①)组成的15μm的第3层作为外层,以无定形聚乙烯[三井石油化学工业(株)制造,商品名:TAFMER A,密度为0.885g/cm3](以下记作PE①)组成的15μm的第2层作为中间层,以线形低密度聚乙烯[三井石油化学工业(株)制造,密度为0.940g/cm3](以下记作L-LDPE①)组成的20μm的第1层作为最内层。
下面,按与本发明1相同的方法成形本发明2-7和比较例1的密封膜。
[本发明2](图1型)
第3层(外层):EVOH①,厚15μm
第2层(中间层):乙烯-乙酸乙烯酯共聚物[三井石油化学工业(株)制造,乙酸乙烯酯(VA):6重量%](以下记作EVA①),厚15μm。
第1层(最内层):线形低密度聚乙烯[三井石油化学工业(株)制造,密度0.923g/cm3](以下记作L-LDPE②),厚20μm。
[本发明3](图2型)
外层(第5层):L-LDPE①,厚15μm
第4层:粘合性聚乙烯[三井石油化学工业(株)制造,商品名:ADMER](以下记作:PE②),厚5μm
第3层:乙烯-乙烯醇共聚物[可乐丽(株)制造(乙烯共聚合摩尔比为29%)](以下记作EVOH②),厚15μm
第2层:PE②,厚5μm
最内层(第1层):L-LDPE①,厚15μm
[本发明4](图2型)
外层(第5层):L-LDPE①,厚10μm
第4层:PE①,厚10μm
第3层:EVOH②,厚10μm
第2层:PE①,厚10μm
最内层(第1层):L-LDPE①,厚10μm
[本发明5](图2型)
外层(第5层):L-LDPE①,厚10μm
第4层:PE②,厚10μm
第3层:EVOH②,厚25μm
第2层:PE②,厚10μm
最内层(第1层):L-LDPE①,厚10μm
[本发明6](图2型)
外层(第5层):L-LDPE①,厚10μm
第4层:PE②,厚5μm
第3层:EVOH②,厚25μm
第2层:PE②,厚5μm
最内层(第1层):L-LDPE①,厚10μm
[本发明7](图1型)
第3层(外层):EVOH①,厚10μm
第2层(中间层):PE②,厚10μm
第1层(最内层):L-LDPE①,厚30μm
[比较例1]
单层(密封膜):L-LDPE①,厚50μm
本发明1-7和比较例1的制造用扁管宽度为240mm的水冷式共挤出吹塑法进行,本发明1-2、7和比较1的薄膜的引出速度是8-10m/分,本发明3-6的薄膜的引出速度是9-13m/分。
[试验例]
用干式层合法将下面记作X的基材薄膜层合在上述本发明1-7的密封膜的外层侧,以该薄膜作为本发明1X-7X。
在本发明1和比较例1的密封膜的外层测层合下面记作Y的基材薄膜,以该薄膜作为本发明1Y、比较例1Y。(这里,本发明1使用干式层合法进行层叠,比较例1使用热封手段进行层合。)
用热封手段在比较例1的密封膜上层合下面记作Z的基材薄膜,以该薄膜作为比较例1Z。
X.L-LDPE①,厚300μm
Y.拉伸尼龙(ONy),15μm/氨基甲酸酯-环氧系树脂(粘合剂)/低密度聚乙烯(LDPE),40μm
Z.聚对苯二甲酸乙二酵酯(PET),12μm/氨基甲酸酯-环氧系树脂(粘合剂)/LDPE,50μm
当本发明的密封膜与上述基材薄膜X-Y层合时,预先将薄膜的层合面进行电晕处理,然后使用通常的干式层合法进行层合。
另外,构成上述基材薄膜的拉伸尼龙(0Ny)薄膜、聚对苯二甲酸乙二醇酯(PET)薄膜、低密度聚乙烯(LDPE)薄膜和用于干式层合法的氨基甲酸酯-环氧系树脂(粘合剂)使用一般的市售品。
使用上述本发明1X-7X、本发明1Y、比较例1Y、比较例1Z的薄膜,成形具有密封膜作为最内层的医疗容器,进行以下的污染实验。
污染实验1:在充填1g效价头孢唑啉钠(以下称为CEZ)的医疗容器(外尺寸(10cm×10cm))的外面涂布或喷雾由DOP(邻苯二甲酸二辛酯、邻苯二甲酸二正丁酯(以下称作DN3P)、邻苯二甲酸二乙酯(以下称作DEP)组成的污染物质后,在40℃、75%RH(相对湿度)条件下保存3个月。用GLC(气相液相色谱法)和GC-MS(气相液相色谱法-质谱法)确认有无污染物质向充填的CEZ转移。
污染实验2:在充填1g效价CEZ的医疗容器的外面喷雾模防锈剂(KG型:神户合成(株)制造)后,在40℃、75%RH条件下保存2周。用GLC和GC-MS法确认有无污染物质向充填的CEZ转移。
污染物质的提取方法和提取物的分析方法:
蒸馏精制特级正己烷(和光纯药(株)制造),去除包含在试剂中的DOP和DNBP的影响。首先,使内容物CEZ完全溶解在10-20ml精制超纯水(商品名,MILLIQ,Millipore有限公司制)中,将该溶液加到用足量精制超纯水洗净的分液漏斗中,加入精制超纯水填到150ml,然后加入150ml蒸馏精制的正己烷。这样,污染物质完全转移到正己烷部分中。将该正己烷部分浓缩至10ml,将其一部分在以下条件下进行GLC分析。
再将剩余的正己烷液浓缩至干,使所得固体再次溶解在0.2ml蒸馏精制的正己烷中,用该溶液进行下述GC-MS分析。
它们的分析结果列于表1-2中。
为了考察在比较例中使用的密封膜L-LDPE①单层薄膜有无污染,由薄膜上裁下约1cm见方的切片,用150ml蒸馏精制的正己烷提取在2g该切片中含有的成分,将该提取液浓缩至干,然后将干固物再次溶解在蒸馏精制的正己烷中,用GLC和GC-MS法进行分析。其结果表明,在上述薄膜中完全不存在污染物质。
[使用的仪器]:Hewlett-Packard公司制造
HP5890系列II气相色谱仪
HP3396系列II积分仪
HP7673控制器
[分析条件]:
以下示出气相色谱分析条件。
柱:超级合金(HT)30m×0.25mm ID×0.25μm
柱温:60℃→10℃/分升温→300℃
柱流量:1.30ml/分
载气:He4.0kg/cm2
注入口温度:200℃
检测器:FID
检测器温度:310℃
灵敏度:RANGE=0 ATT=0
注入方式:无分流高压注入法
注入口压力:30磅/英寸2(0分)-99磅/英寸2/分
-20榜/英寸2(恒定流量)
分流比:38∶1
注入量:1μl溶液[测定条件]GC-MS
装置:HP-5890/5971A-GC-MS(Hewlett-Packard公司
制造)
柱:J & WDB-1×30m×0.25mm×0.25μm
柱温:100℃-10℃/分-280℃
注入口温度:280℃
检测器温度:280℃
检测器:MSD
注入量:2μl无分流
表1污染实验1的结果
DOP | DNBP | DEP | CAP | EPO | ||
本发明1X | GLC | — | — | — | — | — |
GC-MS | — | — | — | — | — | |
本发明2X | GLC | — | — | — | — | — |
GC-MS | — | — | — | — | — | |
本发明3X | GLC | — | — | — | — | — |
GC-MS | — | — | — | — | — | |
本发明4X | GLC | — | — | — | — | — |
GC-MS | — | — | — | — | — | |
本发明5X | GLC | — | — | — | — | — |
GC-MS | — | — | — | — | — | |
本发明6X | GLC | — | — | — | — | — |
GC-MS | — | — | — | — | — | |
本发明7X | GLC | — | — | — | — | — |
GC-MS | — | — | — | — | — | |
本发明1Y | GLC | — | — | — | — | — |
GC-MS | — | — | — | — | — | |
比较例1Y | GLC | ○ | ○ | ○ | ○ | ○ |
GC-MS | ○ | ○ | ○ | ○ | ○ | |
比较例1Z | GLC | ○ | ○ | ○ | — | ○ |
GC-MS | ○ | ○ | ○ | — | ○ |
表2污染实验2的结果
防锈成分 | CAP | EPO | ||
本发明1X | GLC | — | — | — |
GC-MS | — | — | — | |
本发明2X | GLC | — | — | — |
GC-MS | — | — | — | |
本发明3X | GLC | — | — | — |
GC-MS | — | — | — | |
本发明4X | GLC | — | — | — |
GC-MS | — | — | — | |
本发明5X | GLC | — | — | — |
GC-MS | — | — | — | |
本发明6X | GLC | — | — | — |
GC-MS | — | — | — | |
本发明7X | GLC | — | — | — |
GC-MS | — | — | — | |
本发明1Y | GLC | — | — | — |
GC-MS | — | — | — | |
比较例1Y | GLC | ○ | ○ | ○ |
GC-MS | ○ | ○ | ○ | |
比较例1Z | GLC | ○ | — | ○ |
GC-MS | ○ | — | ○ |
CAP:己内酰胺,EP0:环氧化合物
防锈成分:以防锈剂单独分析的峰和碎片数据的保留时间作为比较对象。
表1和表2的符号含义:—(未发现污染物质),○(具有与各污染物质的标准样品相同的保留时间的峰,或者得到的与各污染物质相同的碎片数据)。
本发明提供了在不损害热封性的条件下防污染性优良的密封膜,通过使用包含该密封膜的各种薄膜,可以提供防污染性优良的医疗容器、包装袋、包封。
Claims (11)
1.防污染密封膜,它是以选自线形低密度聚乙烯、低密度聚乙烯、聚丙烯、聚丁烯-1中的至少-种树脂组成的第1层作为最内层的多层密封膜,其特征在于通过由无定形聚烯烃、粘合性聚烯烃或乙烯-乙酸乙烯酯共聚物组成的作为粘合剂层的第2层,在第1层的外侧层合由乙烯-乙烯醇共聚物组成的第3层。
2.权利要求1所述的防污染密封膜,其中第1层由线性低密度聚乙烯或低密度聚乙烯组成,第2层由无定形聚乙烯、粘合性聚乙烯或乙烯-乙酸乙烯酯共聚物组成。
3.权利要求1或2所述的防污染密封膜,其中第1层的厚度是10-40μm,第2层的厚度是5-25μm,第3层的厚度是10-25μm。
4.权利要求1-3中任一项所述的防污染密封膜,其特征在于通过无定形聚烯烃、粘合性聚烯烃或乙烯-乙酸乙烯酯共聚物组成的作为粘合剂层的第4层,在第3层的外测层合选自线形低密度聚乙烯、低密度聚乙烯、聚丙烯、聚丁烯-1中的至少一种树脂组成的第5层。
5.权利要求4所述的防污染密封膜,其中第4层由无定形聚乙烯、粘合性聚乙烯或乙烯-乙酸乙烯酯共聚物组成,第5层由线形低密度聚乙烯或低密度聚乙烯组成。
6.权利要求4或5所述的防污染密封膜,其中第4层的厚度是5-25μm,第5层的厚度是10-40μm。
7.权利要求1-6中任一项所述的防污染密封膜,其中膜的整体厚度是50-80μm。
8.医疗容器用薄膜,它具有权利要求1-7中任一项所述的防污染密封膜作为医疗容器用薄膜的最内层。
9.医疗容器的包装用薄膜,它具有权利要求1-7中任一项所述的防污染密封膜作为包装用薄膜的最内层。
1O.医疗容器的包封用薄膜,它具有权利要求1-7中任一项所述的防污染密封膜作为包封用薄膜的最内层。
11.由权利要求8、9或10所述的膜得到的制品。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4351194 | 1994-03-15 | ||
JP43511/94 | 1994-03-15 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2004100480518A Division CN1636712B (zh) | 1994-03-15 | 1995-03-10 | 医疗容器用、医疗容器的包装用和医疗容器的包封用薄膜 |
Publications (1)
Publication Number | Publication Date |
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CN1128005A true CN1128005A (zh) | 1996-07-31 |
Family
ID=12665767
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2004100480518A Expired - Lifetime CN1636712B (zh) | 1994-03-15 | 1995-03-10 | 医疗容器用、医疗容器的包装用和医疗容器的包封用薄膜 |
CN95190371A Pending CN1128005A (zh) | 1994-03-15 | 1995-03-10 | 防污染密封膜及其制品 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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CN2004100480518A Expired - Lifetime CN1636712B (zh) | 1994-03-15 | 1995-03-10 | 医疗容器用、医疗容器的包装用和医疗容器的包封用薄膜 |
Country Status (14)
Country | Link |
---|---|
US (2) | US20010008686A1 (zh) |
EP (1) | EP0698487B1 (zh) |
JP (1) | JP3263738B2 (zh) |
KR (1) | KR100318654B1 (zh) |
CN (2) | CN1636712B (zh) |
AT (1) | ATE295260T1 (zh) |
AU (1) | AU691261B2 (zh) |
CA (1) | CA2162123C (zh) |
DE (1) | DE69534195T2 (zh) |
DK (1) | DK0698487T3 (zh) |
EG (1) | EG20610A (zh) |
ES (1) | ES2239318T3 (zh) |
TW (1) | TW296355B (zh) |
WO (1) | WO1995025010A1 (zh) |
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CN101028886B (zh) * | 2006-02-27 | 2013-05-01 | 内海企业株式会社 | 集装箱袋用内袋、其制造方法及集装箱袋 |
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KR100318654B1 (ko) | 1994-03-15 | 2002-06-27 | 오츠까 요시미쯔 | 오염방지성 실랜트필름 및 그의 제품 |
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FR2952041B1 (fr) | 2009-10-29 | 2012-02-03 | Sartorius Stedim Biotech Sa | Film multicouche de paroi de poche a soudures destinee a un produit biopharmaceutique. |
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JP3064378B2 (ja) * | 1990-10-11 | 2000-07-12 | 凸版印刷株式会社 | カップ状容器 |
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KR100318654B1 (ko) | 1994-03-15 | 2002-06-27 | 오츠까 요시미쯔 | 오염방지성 실랜트필름 및 그의 제품 |
-
1995
- 1995-03-10 KR KR1019950705083A patent/KR100318654B1/ko not_active IP Right Cessation
- 1995-03-10 CN CN2004100480518A patent/CN1636712B/zh not_active Expired - Lifetime
- 1995-03-10 AU AU18626/95A patent/AU691261B2/en not_active Ceased
- 1995-03-10 AT AT95910799T patent/ATE295260T1/de active
- 1995-03-10 WO PCT/JP1995/000410 patent/WO1995025010A1/ja active IP Right Grant
- 1995-03-10 CA CA002162123A patent/CA2162123C/en not_active Expired - Fee Related
- 1995-03-10 ES ES95910799T patent/ES2239318T3/es not_active Expired - Lifetime
- 1995-03-10 DE DE69534195T patent/DE69534195T2/de not_active Expired - Lifetime
- 1995-03-10 EP EP95910799A patent/EP0698487B1/en not_active Expired - Lifetime
- 1995-03-10 JP JP52394595A patent/JP3263738B2/ja not_active Expired - Lifetime
- 1995-03-10 DK DK95910799T patent/DK0698487T3/da active
- 1995-03-10 CN CN95190371A patent/CN1128005A/zh active Pending
- 1995-03-14 EG EG19895A patent/EG20610A/xx active
- 1995-03-14 TW TW84102419A patent/TW296355B/zh not_active IP Right Cessation
-
1997
- 1997-02-06 US US08/796,755 patent/US20010008686A1/en not_active Abandoned
-
2002
- 2002-12-30 US US10/330,050 patent/US6773775B2/en not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1092593C (zh) * | 1996-02-20 | 2002-10-16 | 出光石油化学株式会社 | 可启开的盖子材料 |
CN100457421C (zh) * | 2004-07-22 | 2009-02-04 | 金德管业集团有限公司 | 一种纯塑防渗氧管及其制备方法 |
CN101028886B (zh) * | 2006-02-27 | 2013-05-01 | 内海企业株式会社 | 集装箱袋用内袋、其制造方法及集装箱袋 |
CN102947383A (zh) * | 2010-06-23 | 2013-02-27 | 住友化学株式会社 | 聚烯烃系树脂组合物、膜、包装材料、多室容器及盖材 |
CN102947383B (zh) * | 2010-06-23 | 2015-02-25 | 住友化学株式会社 | 聚烯烃系树脂组合物、膜、包装材料、多室容器及盖材 |
Also Published As
Publication number | Publication date |
---|---|
KR100318654B1 (ko) | 2002-06-27 |
JP3263738B2 (ja) | 2002-03-11 |
US6773775B2 (en) | 2004-08-10 |
CA2162123C (en) | 2003-12-02 |
AU1862695A (en) | 1995-10-03 |
ES2239318T3 (es) | 2005-09-16 |
CA2162123A1 (en) | 1995-09-21 |
ATE295260T1 (de) | 2005-05-15 |
DE69534195D1 (de) | 2005-06-16 |
WO1995025010A1 (fr) | 1995-09-21 |
EP0698487A1 (en) | 1996-02-28 |
CN1636712A (zh) | 2005-07-13 |
US20010008686A1 (en) | 2001-07-19 |
CN1636712B (zh) | 2010-07-28 |
TW296355B (zh) | 1997-01-21 |
EP0698487A4 (en) | 1997-08-27 |
US20030124329A1 (en) | 2003-07-03 |
DK0698487T3 (da) | 2005-06-06 |
EP0698487B1 (en) | 2005-05-11 |
EG20610A (en) | 1999-09-30 |
AU691261B2 (en) | 1998-05-14 |
DE69534195T2 (de) | 2006-02-16 |
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