CN1392836A - 层合用薄膜及层合体 - Google Patents
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Abstract
对现有的具有由粘接剂组成的粘接层和含有聚丙烯树脂的第1树脂层的层合用薄膜,通过在第1树脂层1与前述粘接层3之间设含有维卡软化点比第1树脂层的维卡软化点低且熔点比第1树脂层的熔点低2℃以上并且厚度是第1树脂层厚度的0.5倍以上的丙烯-α-烯烃共聚物为主剂的第2树脂层,提供形状加工性比现有的层合用薄膜好的层合用薄膜。另外,可提供具有第2树脂层2的层合用薄膜在基材4上形成的层合体5。因此,本发明在产业上的意义重大。
Description
技术领域
本发明涉及粘接固定在基材表面上的层合用薄膜、及层合用薄膜所粘接固定的层合体。更详细地讲,涉及具有包覆基材用聚丙烯树脂层的层合用薄膜、及表面用聚丙烯树脂层包覆的层合体,尤其是涉及通过挤压加工等加工成设定形状的层合处理的金属板、及为形成该层合处理金属板的层合用薄膜。
背景技术
过去,进行了有关在基材表面进行层合的薄膜的研究与开发,特别希望开发粘接性好、在金属基材上粘接固定用的薄膜(以下,称金属层合用薄膜)。金属层合用薄膜主要是防止金属基材腐蚀用的保护薄膜。
近年的发展已能获得与金属板的粘接性好的层合用薄膜(以下,称金属板层合用薄膜)。过去典型的金属板层合用薄膜,是具有聚烯烃组成的树脂层,和对金属有粘接性的粘接剂(以下,称金属用粘接剂)组成的粘接层的2层的两层薄膜。具体地,可列举,作为聚烯烃用聚乙烯、聚丙烯、乙烯-丙烯共聚物的两层薄膜。
上述现有技术的两层薄膜,在加工成设定形状的金属材料表面进行层合时没有产生问题,然而,把层合用薄膜所粘接固定的钢板(以下,称层合钢板)加工成设定的形状,尤其是进行挤压加工时,现有技术的两层薄膜容易引起白化或断裂。具体地讲,用具有现有技术的两层薄膜的层合钢板成型罐时,由于挤压加工中现有技术两层薄膜的白化或断裂,制罐的合格率低。
发明的内容
本发明是鉴于上述现状而完成的研究,其第1目的在于提供在挤压加工等的形状加工中抑制层合用薄膜因白化或断裂而引起的防止腐蚀功能的劣化的层合用薄膜。另外,本发明的第2目的在于提供有关上述本发明的层合用薄膜粘接固定的层合体。以下,依次说明上述层合用薄膜和上述层合体。(I)层合用薄膜
为了达到上述第1目的,本发明提供具有由粘接剂组成的粘接层、和在粘接层上形成的有聚丙烯树脂的第1树脂层、及在第1树脂层与粘接层之间形成的维卡软化点比前述第1树脂层的维卡软化点低且熔点比前述第1树脂层的熔点低2℃以上而且厚度是第1树脂层厚度的0.5倍以上的丙烯-α-烯烃共聚物为主剂的第2树脂层的层合用薄膜。本发明的层合用薄膜,其特征在于,上述粘接层与上述第1树脂层之间设有上述第2树脂层。
上述第1树脂层是只含聚丙烯树脂的层,或是含聚丙烯树脂和添加剂的层。第1树脂层是含聚丙烯树脂和添加剂的层时,要注意实质上含聚丙烯树脂且含微量的添加剂。作为聚丙烯树脂,可列举NMR五单元组比例相同的丙烯均聚物构成的树脂,或NMR五单元组比例不同的多种丙烯均聚物共混的树脂。
作为上述第2树脂层,具体地可列举只由丙烯-α-烯烃共聚物组成的树脂层,只由丙烯与α-烯烃共聚物橡胶的共聚物组成的树脂层,丙烯-α-烯烃共聚物与橡胶物质的混合物质组成的树脂层、或丙烯与α-烯烃共聚物橡胶的共聚物和橡胶物质的混合物质组成的树脂层。另外,上述第2树脂层也包括还含有石油树脂的树脂层、还含有松香、松香酯或萜烯树脂、或它们的加氢物的树脂层。
本说明书中的所谓「丙烯-α-烯烃共聚物」是丙烯与丙烯以外的α-烯烃的共聚物,例如,可列举丙烯与丙烯以外的1种α-烯烃的两成分组成的共聚物,或丙烯与、和丙烯不同且彼此也不同的几种α-烯烃的三种以上的成分组成的共聚物。又,所谓共聚物,是无规共聚物、嵌段共聚物及接枝共聚物的总称。具体地,作为丙烯-α-烯烃共聚物可列举丙烯-乙烯无规共聚物、丙烯-丁烯无规共聚物、丙烯-乙烯嵌段共聚物、丙烯-乙烯-丁烯无规共聚物。另外,本说明书中所谓「丙烯与α-烯烃共聚物橡胶的共聚物」,意味着丙烯与α-烯烃共聚物橡胶的嵌段聚合物或聚丙烯与α-烯烃共聚物橡胶的接枝共聚物。另外,本说明书中的所谓「橡胶物质」意味着包含橡胶类的1种橡胶物质。此外,上述第2树脂层也可以含有多种类的橡胶物质,作为橡胶类可列举,乙烯-丙烯橡胶、乙烯-丁烯橡胶、丙烯-丁烯橡胶、加氢苯乙烯-二烯橡胶。另外,本说明书中的所谓「石油树脂」,是以提炼石油中乙烯所用乙烯装置副产的单烯烃类或二烯烃类为主的馏分进行聚合所得聚合物的集合体及对该聚合物加氢的加氢类聚合物(加氢聚合物)的集合体。而,石油树脂是脂肪族石油树脂、芳香族石油树脂及脂环族石油树脂的总称。
上述粘接剂含有酸改性丙烯聚合物时,可确保上述粘接层与金属基材的粘接性,因此,可提供金属层合用薄膜。本说明书中的所谓「酸改性丙烯聚合物」意味着丙烯聚合物的基本成分(聚合单元)被酸成分置换,或丙烯聚合物的一部分被酸成分置换的聚合物。另外,本说明书的所谓「丙烯聚合物」意味着聚丙烯或丙烯为主成分的丙烯共聚物。因此,作为酸改性丙烯聚合物,可列举酸改性的丙烯均聚物、酸改性的丙烯-α-烯烃共聚物。
上述第1树脂层的熔点若是155℃以上,则可提供通过熔接粘接固定在基材上的层合用薄膜。由此,在熔接工序中,可抑制粘在加热装置或冷却装置上。因此,可形成用表面平滑性好的层合用薄膜所包覆的基材。
当上述第1树脂层和上述第2树脂层及粘接层的任一层含有氧化锌微细粒子时,成为可抑制硫化物透过的层合用薄膜。这是因为氧化锌微细粒子具有吸附硫化氢等硫化物特性的缘故。(II)层合体
为达到上述第2的目的,本发明提供具有基材和在基材表面形成的由粘接剂组成的粘接层、及在粘接层上形成的含有聚丙烯树脂的第1树脂层和在粘接层与第1树脂层之间形成的含有维卡软化点比第1树脂层的维卡软化点低且熔点比第1树脂层的熔点低2℃以上且厚度是第1树脂层厚度的0.5倍以上的丙烯-α-烯烃共聚物为主剂的第2树脂层的层合体。本发明的层合体,其特征是,在基材表面形成的层合用薄膜在粘接层与第1树脂层之间有第2树脂层。
上述基材是钢板,且上述粘接剂含有酸改性聚丙烯,并且,上述第1树脂层若是155℃以上的熔点及有0.1μm~10μm的厚度时,即使进行挤压加工等的形状加工,第1树脂层也不会白化或断裂,可提供形状加工性好的层合钢板。
本说明书中的所谓「钢板」,意味着铁板、铁基合金板、镀金属的铁板或镀金属的铁基合金板、或者这些的表面处理板。此处,所谓表面处理主要是为了提高粘接强度,将表面进行改质的处理。作为钢板,具体地可列举铁板、无锡钢板、镀锡钢板(马口铁)、镀镍钢板、镀铬钢板、锚定处理钢板、底面处理钢板。采用挤压加工进行形状加工时,通常用0.1~5mm左右厚的钢板。
若上述粘接层和前述第1树脂层及前述第2树脂层的任一层还含有氧化锌微细粒子时,可提供对硫化氢等的硫化物的耐腐蚀性好的层合体。
附图的简单说明
图1是示意性表示本发明的层合用薄膜的一个例子的截面图。
图2是示意性表示本发明的层合体的一个例子的截面图。
图3是示意地表示的说明挤压加工的立体图。
实施发明的最佳方案
(I)根据图1说明本发明的层合用薄膜。图1是示意性表示本发明的层合用薄膜的一个例子的截面图。在层合用薄膜的制造中,也可以利用制造层合薄膜用的任何公知技术,从制造各层的厚度及该厚度均匀性好的层合用薄膜的观点来看,优选使用共挤出方法及共拉伸方法。使用共挤出方法及共拉伸方法时,可简便地形成所要求厚度的双向拉伸薄膜,而且,生产成本也可控制得很低。
作为第1树脂层1,最好是NMR五单元组比例在97%以上、更好是98%以上的丙烯均聚物、与NMR五单元组比例是96%以下、更好是95%以下的丙烯均聚物的混合物组成的层。通过用上述混合物,不仅确保耐热性,而且,可形成在成型罐时所进行的挤压加工中更难引起断裂及白化的层合用薄膜。混合物中NMR五单元组比例在97%以上的丙烯均聚物的含量为5~90%,优选15~70%,更优选30%~50%。含量低于5%时,耐热性不够,而含量在90%以上时,虽然耐热性好,但挤压加工中容易引起层合用薄膜的断裂或白化。
第1树脂层1的厚度为0.1~10μm,优选0.2~5μm,更优选0.4~3μm。低于0.1μm时,在层合处理中的加热或冷却时容易粘在机器上,而超过10μm时,在挤压加工中更容易引起薄膜的断裂或白化。
对作为形成第2树脂层2的材料物质优选的种类,及混合物质组成的第2树脂层2时各材料物质的优选含量也进行说明。作为第2树脂层2,优选丙烯-乙烯嵌段共聚物组成的树脂层,丙烯与乙烯-丙烯橡胶的共聚物组成的树脂层、或丙烯-α-烯烃共聚物与乙烯-丙烯橡胶的混合物组成的树脂层。更优选丙烯-乙烯-丁烯无规共聚物与乙烯-丙烯橡胶的混合物组成的树脂层。另外,橡胶物质对构成第2树脂层2的混合物质的含量优选5重量%~45重量%。
上述第2树脂层2还含石油树脂时,作为种类,使用维卡软化点110℃~150℃、优选115℃~145℃、更优选120℃~140℃的加氢石油树脂(加氢石油树脂),而作为含量,调整到1重量%~30重量%、优选2重量%~20重量%、更优选3重量%~15重量%。如上述第2树脂层2含石油树脂时,由于石油树脂的混合,第2树脂层2内非晶部分增多。如果第2树脂层2内的非晶部分增多,则在基材上进行层合时的加热及冷却中,第2树脂层2原有的取向便平稳而迅速地被松弛。因此,通过取向的松弛,在挤压加工等对层合体的形状加工中,可减少第1树脂层1的白化或断裂。另外,通过取向的松弛,即使在具有采用拉伸方法工序的层合用薄膜的制造中,也可显著地提高拉伸稳定性及厚度精确度。此外,第2树脂层也可以含有松香、松香酯、萜烯树脂或它们的加氢物等。含有松香或松香酯、萜烯树脂或它们的加氢物等时,与含有石油树脂的情形达到同样的效果。
第2树脂层2的维卡软化点(一般,也称维卡软化温度)比第1树脂层1的维卡软化点低时,在形状加工时难以引起第1树脂层的白化或断裂。然而,第2树脂层2的维卡软化点高于160℃时,在形状加工时易引起白化或断裂,而第2树脂层2的维卡软化点低于80℃时,在成膜中膜厚的均匀性或膜质量的稳定性等方面产生问题。例如,在层合用薄膜的制造中进行挤出时,由于挤出而形成膜厚不均匀的薄膜,而在层合用薄膜的制造中进行拉伸时,由于拉伸而产生白化或断裂。因此,作为第2树脂层2,优选维卡软化点在80℃以上且160℃以下的树脂层,更优选维卡软化点80℃以上且130℃以下的树脂层。
第2树脂层2的熔点比第1树脂层的熔点低2℃以上时,在形状加工时难以引起第1树脂层1的白化或断裂。作为第2树脂层2,优选熔点比第1树脂层1低10℃以上的树脂层,更优选熔点比第1树脂层1低20℃以上的树脂层。然而,第2树脂层2的熔点比第1树脂层1的熔点低60℃以上时,由于成膜中膜厚的均匀性或膜质量的稳定性等方面容易产生问题,故优选第2树脂层2的熔点与第1树脂层熔点的温度差在60℃以下。
第2树脂层2的厚度不足第1树脂层1厚度的0.5倍时,进行形状加工时不能充分抑制第1树脂层1的白化或断裂。因此,优选第2树脂层2的厚度为第1树脂层1厚度的0.5倍以上。
作为粘接层3的酸改性丙烯聚合物,从与金属基材的粘接强度的观点考虑,优选酸改性丙烯均聚物,最优选熔体流动速率(MFR)1~30g/10min(MFR测定条件:230℃,21.18N)的丙烯均聚物,另外,作为酸成分,优选不饱和羧酸或不饱和羧酸酐,最优选马来酸酐。作为酸改性丙烯聚合物,酸成分对丙烯聚合物的含量优选0.05重量%以上且0.45重量%以下。
对酸改性丙烯以外的构成粘接剂的物质进行说明。作为粘接剂的基剂,例如,可列举丙烯-α-烯烃共聚物。粘接剂只要含有酸改性丙烯,就还可以含有用于提高与金属基材粘接性的乙烯-醋酸乙烯酯共聚物及其酸改性物质或乙烯-(甲基)丙烯酸酯共聚物及其酸改性物质。另外,粘接剂还可以含有无机物质组成的抗粘连剂(防止粘连剂)。作为无机物质组成的抗粘连剂,可列举无定形二氧化硅、长石、云母或氧化锌。
优选粘接剂是酸改性丙烯均聚物、丙烯-乙烯-丁烯无规共聚物(乙烯含量0.5~10重量%、丁烯含量0.5~10重量%)和乙烯-(甲基)丙烯酸甲酯共聚物((甲基)丙烯酸甲酯含量10~30重量%)、及抗粘连剂的混合物。此处,圆括弧()内所示的含量是以各物质为基准的含量,例如,「A-B共聚物(B含量1~2重量%)」意味着B相对于A-B共聚物总量的含量是1~2重量%。更优选该混合物质完全满足下述条件的情况。再者,在各条件中的含量是对粘接剂总量的含量。
(条件1)酸改性丙烯均聚物的含量是30~47重量%,(条件2)丙烯-乙烯-丁烯无规共聚物的含量是47~69重量%,(条件3)乙烯-(甲基)丙烯酸甲酯共聚物的含量是0.1~4重量%,(条件4)抗粘连剂的含量是0.05~5重量%。
接粘层3的厚度为0.2~50μm,优选0.5~20μm,更优选0.8~10μm。不足0.2μm时,与金属基材的粘接强度低,在挤压加工等中易剥离。即使形成50μm以上厚度的粘接层,由于粘接强度对厚度已饱和,成本的增加是不必要的。故应根据进行哪种形状加工确定适当的厚度。
对粘接层3和第1树脂层1及第2树脂层2的至少任一层再进一步含有氧化锌微粒的情况进行说明。由于氧化锌微细粒子具有吸附硫化氢等硫化物的特性,故可提供阻隔硫化物的层合用薄膜。以下列举具体例。不含氧化锌粒子的层合用薄膜即使层合在罐的内面,当内容物是大马哈鱼或鳟等的醋渍食品等时,由内容物产生的硫化氢透过层合用薄膜使金属基材的表面变黑。然而,使用可抑制硫化物透过的层合用薄膜时,即使是内容物大马哈鱼或鳟的醋渍品等产生硫化氢的情况,也可抑制金属基材表面黑化等的变色。
氧化锌微细粒子的浓度如果是0.001g/m2~15g/m2、优选0.01g/m2~10g/m2、更优选0.05g/m2~1g/m2,则有效地体现吸附硫化氢的功能。氧化锌微细粒子的添加量不足0.001g/m2时,不能充分地体现吸附硫化氢的功能,而超过15g/m2时,透明性、平滑性、光泽性等层合用薄膜本身的特性恶化。
另外,由于氧化锌微细粒子也具有作为抗粘连剂的功能,故优选在粘接层3中添加氧化锌微细粒子。然而,只在粘接层3中添加超过15g/m2的氧化锌微细粒子时,粘接强度降低。因此,只要是不防碍粘接强度,优选只在粘接层3中添加氧化锌微细粒子,在仅粘接层3不能阻隔硫化物的情况下,也可在第1树脂层1或第2树脂层2中添加氧化锌微细粒子。
粘接层3中含的氧化锌微细粒子(一般称二级粒子)的平均粒径如果是0.5μm~5μm,则在硫化物的阻隔性方面最佳。此外,在形成薄膜的过程中,氧化锌微细粒子的粒径发生变化。因此,为获得上述的最佳二级粒子,作为原料的氧化锌微细粒子(一般称初级粒子),最好用平均粒径10nm~100nm的氧化锌微细粒子。(实施例I-1)
在240℃下共挤出第1树脂层1的材料物质和第2树脂层2的材料物质及粘接层3的材料物质,形成层合薄膜。然后,在110℃下将层合薄膜沿纵向滚辗拉延5倍后,在130℃下沿横向拉幅拉延9倍,制得厚度30μm的层合用薄膜。而制得的层合用薄膜中第1树脂层1的厚度、第2树脂层2的厚度及粘接层3的厚度分别是2μm、23μm及5μm。
作为第1树脂层1的材料物质,使用了含第1的丙烯均聚物(NMR五单元组比例:98.5%,MFR:5g/10min(230℃,21.18N),熔点:167℃)35重量%、第2的丙烯均聚物(NMR五单元组比例:94.0%,MFR:3g/10min(230℃、21.18N),熔点:162℃)65重量%的混合物质。而,作为第2树脂层2的材料物质,使用了含丙烯-乙烯-丁烯无规共聚物(乙烯含量:2.2重量%,1-丁烯含量:2.7重量%,MFR:2g/10min(230℃,21.18N),维卡软化点:128℃,熔点:140℃)70重量%、乙烯-丙烯橡胶(乙烯含量:70重量%,MFR:2g/10min(190℃,21.18N),维卡软化点:90℃)30重量%的混合物质。另外,作为粘接层3的材料物质,使用了含丙烯均聚物(MFR:5g/10min(230℃,21.18N),熔点:160℃)为基础聚合物的改性率0.2重量%的马来酸酐改性聚丙烯40重量%、丙烯-乙烯-丁烯无规共聚物(乙烯含量:2.2重量%,1-丁烯含量:2.7重量%,MFR:2g/10min(230℃,21.18N))56重量%、乙烯-丙烯酸甲酯共聚物(丙烯酸甲酯含量:20摩尔%,MFR:20g/10min(190℃,21.18N))2重量%、无定形二氧化硅2重量%的混合物质。(实施例I-2)
除了使第1树脂层1的厚度为1μm、第2树脂层2的厚度为16μm、粘接层3的厚度为3μm、总厚度为20μm、且在粘接层3的粘接剂中添加2.5重量%(相当于0.068g/m2)的氧化锌微细粒子(初级粒子的平均粒径30nm,比表面积30m2/g)以外,其他与实施例I-1同样地制造层合用薄膜。
(II)根据图2说明本发明的层合体。层合体具有在基材表面粘接固定的上述本发明的层合用薄膜。因此,省略说明有关层合用薄膜。
基材与层合用薄膜的粘接,可利用公知技术进行。作为公知技术,具体地可列举压接法或熔敷法。层合体在后面进行形状加工时,优选用热辊的熔敷或用喷灯的熔敷。再者,适当采用熔敷方法时,也可按照需要将基材和层合用薄膜进行预加热。又,用热辊进行熔敷时,层合温度(熔敷温度)为100℃~300℃、优选120℃~200℃、更优选130℃~170℃。(实施例II-1)
将上述实施例I-1的层合用薄膜和厚0.2mm的无锡钢板4用160℃的热辊进行熔敷制造层合钢板。将层合用薄膜与无锡钢板4的粘接强度示于表1。又,用挤压加工(参照图3)将本实施例的层合钢板5进行制罐时的合格率也示于表1。
此处,层合用薄膜与无锡钢板4的粘接强度,在试样宽1cm、拉伸速度200mm/min的条件下通过进行180°的剥离进行测定。另外,所谓合格率,意味着在采用挤压加工将层合钢板进行制罐时,层合用薄膜不产生白化或断裂的比例(用投入数除合格数的值)。合格率的测定中,使层合用薄膜与无锡钢板4构成的层合钢板5,其层合用薄膜为内面,挤压加工成直径100mm、深40mm的圆罐。(比较例II-1)
首先,除了使第1树脂层1的厚度为12μm,第2树脂层2的厚度为13μm、粘接层3的厚度为5μm以外,其他与实施例I-1同样地制造层合用薄膜。然后,用本比较例的层合用薄膜和厚0.2mm的无锡钢板,与上述实施例II-1同样地制造层合钢板5。
对本比较例的层合钢板5,将层合用薄膜与无锡钢板4的粘接强度及制罐时的合格率示于表1。由表1可知,本比较例的合格率比上述实施例II-1的合格率低。这是因为第1树脂层1的厚度厚达12μm的缘故。(比较例II-2)
首先,除了使第1树脂层1的厚度为23μm、第2树脂层2的厚度为2μm、粘接层3的厚度为5μm以外,其他与实施例I-1同样地制造层合用薄膜。然后,用本比较例的层合用薄膜和厚0.2mm的无锡钢板4,与上述实施例II-1同样地制造层合钢板5。
对本比较例的层合钢板5,将层合用薄膜与无锡钢板4的粘接强度及制罐时的合格率示于表1。由表1可知,本比较例中的合格率比上述实施例II-1的合格率低得多。这是因为第1树脂层1的厚度为23μm,而第2树脂层2的厚度(第1树脂层1厚度的0.08倍)又薄的缘故。(比较例II-3)
除了用丙烯-乙烯无规共聚物(乙烯含量:0.5重量%、MFR:2g/10min(230℃,21.18N),熔点:158℃)作为第1树脂层1的材料物质,用丙烯均聚物(NMR五单元组比例:98.5%,MFR:5g/10min(230℃,21.18N),维卡软化点:162℃,熔点:167℃)作为第2树脂层2的材料物质以外,其他与上述实施例I-1同样地制造层合用薄膜。然后,用本比较例的层合用薄膜和厚0.2mm的无锡钢板,与上述实施例II-1同样地制造层合钢板。
对本比较例的层合钢板5,将层合用薄膜与无锡钢板4的粘接强度以及制罐时的合格率示于表1。由表1可知,与上述实施例II-1中的合格率相比,本比较例中的合格率极低。这是因为第2树脂层2的维卡软化点比第1树脂层1的维卡软化点高且熔点也比第1树脂层1的熔点高的缘故。(实施例II-2)
用上述实施例I-2中的层合用薄膜和厚0.2mm的无锡钢板4,与上述实施例II-1同样地制造层合钢板5。将本实施例的层合用薄膜与无锡钢板4的粘接强度示于表1。然后,与上述实施例II-1同样地,用挤压加工将本实施例的层合钢板制罐。将制罐时的合格率示于表1。
此外,在10个合格的罐中加入大马哈鱼的醋渍品后,由盖密封后在常温下放置,2个月后开罐,观察罐内面的状态,结果对整个的罐没发现颜色的变化。
再者,只要不脱离本发明的要旨,也可以在第1树脂层1、第2树脂层2和/或粘接层3中混入白色微细粉末。特别是食品罐头等的情况,即使用添加有认为可充分吸附可能产生的硫化物量的氧化锌微细粒子的层合用薄膜,虽然内容物的质量没有问题,但罐的内表面也有可能引起变色。如果使白色微细粉末混入层合用薄膜中,则可看不见罐内表面意外的变色。由此可避免消费者对本来没问题的内容物的质量因发现罐内的变色而担心的问题。作为白色微细粉末,例如,可列举氧化钛、滑石、碳酸钙等。另外,白色微细粉末的添加量,应考虑所使用白色微细粉末的颜色的遮蔽性后来决定。(比较例II-4)
除了不添加氧化锌微细粒子外,其他与上述实施例I-2同样地制造层合用薄膜。然后,用本比较例的层合用薄膜和0.2mm厚的无锡钢板4,与上述实施例II-2同样地制造层合钢板5,再用挤压加工制罐。将本比较例的层合用薄膜与无锡钢板的粘接强度及制罐时的合格率示于表1。
此外,在10个合格的罐中加入大马哈鱼的醋渍品后,用盖密封后在常温下放置。2个月后开罐,观察罐内面的状态,结果发现10个中有9个为褐色或黑色着色。而另外的1个也有颜色,是黄色。表1
粘接强度(N/cm) | 合格率 | |
实施例II-1 | 18.2 | 0.99 |
比较例II-1 | 17.1 | 0.33 |
比较例II-2 | 16.8 | 0.01 |
比较例II-3 | 17.8 | 0.01 |
实施例II-2 | 13.3 | 0.99 |
比较例II-4 | 13.7 | 0.99 |
产业上的利用可能性
如以上说明,根据本发明的构成,可提供比现有的层合用薄膜形状加工性好的层合用薄膜。另外,可提供形状加工性好的层合用薄膜在基材上形成的层合体。因此,可充分完成本发明的各课题。
另外,通过在层合用薄膜中混入氧化锌微细粒子,可提供形状加工性及硫化氢等硫化物阻隔性好的层合用薄膜,以及形状加工性及对硫化物的耐腐蚀性好的层合体。
因此,本发明在产业上的意义很大。
Claims (11)
1.一种层合用薄膜,其含有由粘接剂组成的粘接层,和在前述粘接层上形成的含有聚丙烯树脂的第1树脂层、及在前述第1树脂层和前述粘接层之间形成的含有维卡软化点比前述第1树脂层的维卡软化点低且熔点比前述第1树脂层的熔点低2℃以上、厚度是前述第1树脂层厚度的0.5倍以上的丙烯-α-烯烃共聚物为主剂的第2树脂层。
2.权利要求1记载的层合用薄膜,其特征在于,前述粘接剂含有酸改性丙烯聚合物。
3.权利要求2记载的层合用薄膜,其特征在于,前述第1树脂层的熔点是155℃以上。
4.权利要求3记载的层合用薄膜,其特征在于,前述第1树脂层的厚度是0.1μm~10μm,且,前述粘接层的厚度是0.2μm~50μm。
5.权利要求4记载的层合用薄膜,其特征在于,前述第2树脂层还含有橡胶物质。
6.权利要求4记载的层合用薄膜,其特征在于,前述第2树脂层还含有由石油树脂、松香、松香酯、萜烯树脂、加氢松香、加氢松香酯及加氢萜烯树脂组成的组中选出的至少1种的物质。
7.权利要求4记载的层合用薄膜,其特征在于,前述第1树脂层的聚丙烯树脂由NMR五单元组比例为97%以上的丙烯均聚物与NMR五单元组比例小于97%的丙烯均聚物的混合物构成。
8.权利要求4记载的层合用薄膜,其特征在于,前述粘接层和前述第1树脂层及前述第2树脂层的任一层还含有氧化锌微细粒子。
9.一种层合体,其含有基材、在前述基材的表面形成的由粘接剂构成的粘接层、及在前述粘接层上形成的含有聚丙烯树脂的第1树脂层、和在前述粘接层与前述第1树脂层之间形成的含有维卡软化点比第1树脂层的维卡软化点低且熔点比第1树脂层的熔点低2℃以上且厚度是第1树脂层厚度的0.5倍以上的丙烯-α-烯烃共聚物为主剂的第2树脂层。
10.权利要求9记载的层合体,其特征在于,前述基材是钢板,且前述粘接剂含有酸改性丙烯聚合物,又,前述第1树脂层具有155℃以上的熔点及0.1μm~10μm的厚度。
11.权利要求10记载的层合体,其特征在于,前述粘接层与前述第1树脂层和前述第2树脂层中的任一层还含有氧化锌微细粒子。
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CN100419964C (zh) * | 2003-10-24 | 2008-09-17 | 日东电工株式会社 | 切片用粘着片、切片方法和半导体元件的制造方法 |
CN103584531A (zh) * | 2007-08-24 | 2014-02-19 | 雷奥两合股份公司 | 家具的边缘嵌条 |
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GB0102228D0 (en) | 2001-01-29 | 2001-03-14 | Gluco Ltd | Adhesive |
CN1852661B (zh) * | 2003-08-14 | 2010-08-18 | 嘉吉有限公司 | 含有莫那甜的口香糖组合物及其制造方法 |
US8272511B2 (en) * | 2004-10-22 | 2012-09-25 | The Procter & Gamble Company | Packaging and disposable article disposed therein |
US7473750B2 (en) * | 2004-12-07 | 2009-01-06 | Fina Technology, Inc. | Random copolymers and formulations useful for thermoforming and blow molding applications |
US7638204B2 (en) * | 2006-02-28 | 2009-12-29 | Illinois Tool Works Inc. | Tier sheet |
WO2007133383A1 (en) * | 2006-05-09 | 2007-11-22 | Dow Global Technologies Inc. | Multilayer adhesive polymer film |
US9752022B2 (en) | 2008-07-10 | 2017-09-05 | Avery Dennison Corporation | Composition, film and related methods |
KR100966985B1 (ko) * | 2008-08-12 | 2010-06-30 | 스미토모 베이클리트 컴퍼니 리미티드 | 전자 부품 포장용 커버 테이프 및 전자 부품 포장체 |
ES2712893T3 (es) | 2010-03-04 | 2019-05-16 | Avery Dennison Corp | Película exenta de PVC y película laminada exenta de PVC |
WO2015102859A1 (en) | 2013-12-30 | 2015-07-09 | Avery Dennison Corporation | Polyurethane protective film |
JP6520952B2 (ja) * | 2014-09-18 | 2019-05-29 | 三菱ケミカル株式会社 | 光架橋性透明粘着材、透明粘着材積層体及び光学装置構成用積層体 |
JP6657732B2 (ja) * | 2015-10-02 | 2020-03-04 | 大日本印刷株式会社 | 金属端子用接着性フィルム |
CN108026344B (zh) * | 2016-09-01 | 2021-06-29 | 理研科技株式会社 | 树脂组合物以及使用该树脂组合物的层叠体 |
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JPS62230876A (ja) * | 1986-03-31 | 1987-10-09 | Nitto Electric Ind Co Ltd | 熱硬化性防食テ−プ |
GB8724243D0 (en) * | 1987-10-15 | 1987-11-18 | Metal Box Plc | Laminates of polyolefin-based film |
JPH11500077A (ja) * | 1995-02-17 | 1999-01-06 | ザ ダウ ケミカル カンパニー | 金属に貼合せるための保護ポリマーフィルム |
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JP4576640B2 (ja) * | 1998-07-15 | 2010-11-10 | 凸版印刷株式会社 | 化粧シート |
DE19936304A1 (de) | 1998-09-19 | 2000-03-23 | Alkor Gmbh | Mehrschichtige thermoverformbare Möbelkunststoffverbundfolie oder damit hergestellte Möbelteile sowie Verfahren zur Herstellung der Möbel-Kunststoffverbundfolie |
JP2000109066A (ja) * | 1998-09-30 | 2000-04-18 | Nkk Corp | 内容物保護性に優れた一般缶用樹脂被覆鋼板および樹脂フィルム |
JP3353735B2 (ja) * | 1999-02-26 | 2002-12-03 | 日本鋼管株式会社 | 樹脂被覆鋼板 |
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CN100419964C (zh) * | 2003-10-24 | 2008-09-17 | 日东电工株式会社 | 切片用粘着片、切片方法和半导体元件的制造方法 |
CN103584531A (zh) * | 2007-08-24 | 2014-02-19 | 雷奥两合股份公司 | 家具的边缘嵌条 |
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US6713166B2 (en) | 2004-03-30 |
US20020187323A1 (en) | 2002-12-12 |
CA2392455A1 (en) | 2002-04-04 |
EP1273437A4 (en) | 2003-09-10 |
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