CN112004902A - 粘接性树脂组合物和叠层体 - Google Patents
粘接性树脂组合物和叠层体 Download PDFInfo
- Publication number
- CN112004902A CN112004902A CN201980027443.0A CN201980027443A CN112004902A CN 112004902 A CN112004902 A CN 112004902A CN 201980027443 A CN201980027443 A CN 201980027443A CN 112004902 A CN112004902 A CN 112004902A
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- China
- Prior art keywords
- ethylene
- layer
- ethylene polymer
- laminate
- resin composition
- Prior art date
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- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C—CHEMISTRY; METALLURGY
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
本发明的粘接性树脂组合物的特征在于:含有包含利用不饱和羧酸或其衍生物进行接枝改性的乙烯系聚合物的乙烯系聚合物(A),并且该组合物满足下述的条件(1)~(4)。(1)基于ASTMD1238测得的温度190℃、2160g负荷下的熔体流动速率(MFR)为0.1~3g/10分钟。(2)密度为910~930kg/m3。(3)在结晶洗脱分级色谱测定中,在50℃以下的洗脱成分的比率为20质量%以上。(4)在结晶洗脱分级色谱测定中,在90℃以上的洗脱成分的比率为25质量%以上。本发明的粘接性树脂组合物对于乙烯-乙烯醇共聚物等阻气性树脂具有优异的粘接力。因此,包含含有上述粘接性树脂组合物的粘接层和与该粘接层直接相接的阻气性树脂层的叠层体,即使是为了使阻气性树脂层柔软化而添加有添加剂的情况等,由于上述两层牢固粘接,上述两层间也不易发生剥离。因此,上述叠层体能够有效地用作具有高阻隔性的包装和容器等。
Description
技术领域
本发明涉及粘接性树脂组合物和叠层体,详细而言,涉及对阻气性树脂具有高的粘接性的粘接性树脂组合物和包含含有该粘接性树脂组合物的层的阻隔性高的叠层体。
背景技术
聚乙烯由于透明性、柔软性、卫生性、加工性等优异,并且廉价,已广泛用作各种食品和化学品等的包装或容器。
聚乙烯由于气体透过性大,因此无法单独用作包装和容器。因此,大多情况下在聚乙烯上叠层阻气性高的其他材料、例如聚酰胺或乙烯-乙烯醇共聚物等阻气性树脂后,作为包装和容器使用。另外,聚乙烯由于为无极性材料,几乎没有粘接力,因此在将聚乙烯叠层在阻气性树脂上的方面,进行了各种改良。
例如,在专利文献1中公开了一种将含有乙烯系聚合物和改性乙烯系聚合物的聚乙烯树脂组合物的层与乙烯-乙酸乙烯酯共聚物的皂化物、聚酰胺、聚酯等的层叠层而成的叠层体。在专利文献1中记载了上述树脂组合物对其他树脂的粘接性优异,该粘接性也不会因热、水、盐水等而劣化的内容。
另一方面,如今在降低食品浪费的要求加重的情况下,食品包装材料的高阻隔化的趋势发展,对于乙烯-乙烯醇共聚物等阻气性树脂要求更高阻气性。根据该要求,近年来使阻气性树脂低乙烯化而提高阻气的倾向正在增强。
然而,作为阻气性树脂的乙烯-乙烯醇共聚物等在低乙烯化时会变得又硬又脆,因此为了使其柔软化,采取了向乙烯-乙烯醇共聚物等中添加添加剂(苯乙烯系弹性体等)的措施(专利文献2、3)。然而,这样一来,添加剂会妨碍与聚乙烯的粘接,因此利用现有的粘接性树脂时,聚乙烯与阻气性树脂的粘接力不足的情况有所增多。
现有技术文献
专利文献
专利文献1:日本特开昭59-068351号公报
专利文献2:日本特开2010-254968号公报
专利文献3:日本特开2011-202147号公报
发明内容
发明所要解决的技术问题
本发明的目的在于:提供一种与乙烯-乙烯醇共聚物等阻气性树脂的粘接力优异的粘接性树脂。
用于解决技术问题的技术方案
实现上述目的的本发明为下述[1]~[9]。
[1]一种粘接性树脂组合物,其特征在于:含有包含利用不饱和羧酸或其衍生物进行接枝改性的乙烯系聚合物的乙烯系聚合物(A),并且该组合物满足下述的条件(1)~(4)。
(1)基于ASTMD1238测得的温度190℃、2160g负荷下的熔体流动速率(MFR)为0.1~3g/10分钟。
(2)密度为910~930kg/m3。
(3)在结晶洗脱分级色谱测定中,在50℃以下的洗脱成分的比率为20质量%以上。
(4)在结晶洗脱分级色谱测定中,在90℃以上的洗脱成分的比率为25质量%以上。
[2]如[1]所述的粘接性树脂组合物,其特征在于:上述乙烯系聚合物(A)含有下述的乙烯系聚合物(A1)20~40质量%和乙烯系聚合物(A2)60~80质量%〔其中,将乙烯系聚合物(A1)和乙烯系聚合物(A2)的合计设为100质量%〕,上述乙烯系聚合物(A1)和乙烯系聚合物(A2)中的至少一者包含利用不饱和羧酸或其衍生物进行接枝改性的乙烯系聚合物。
(A1)密度为930~965kg/m3且基于ASTMD1238测得的温度190℃、2160g负荷下的熔体流动速率(MFR)为0.1~10g/10分钟的乙烯系聚合物。
(A2)密度为858~929kg/m3且基于ASTMD1238测得的温度190℃、2160g负荷下的熔体流动速率(MFR)为0.1~10g/10分钟的乙烯系聚合物。
[3]一种叠层体,其特征在于:叠层有:含有乙烯系聚合物的层(I);含有[1]或[2]所述的粘接性树脂组合物的粘接层(II);以及含有乙烯-乙烯醇共聚物的层(III)和/或含有聚酰胺树脂的层(IV),并且上述层(II)与层(III)和层(IV)中的至少一者直接相接。
[4]如[3]所述的叠层体,其中,上述乙烯-乙烯醇共聚物为将源自乙烯的结构单元的含有率为20~30摩尔%的乙烯-乙酸乙烯酯共聚物皂化而得到的聚合物。
[5]如权利要求3所述的叠层体,其中,上述层(III)还含有苯乙烯系弹性体10~40质量%。
[6]如[3]~[5]中任一项所述的叠层体,其中,上述聚酰胺树脂含有尼龙6、尼龙66、尼龙610、尼龙12、尼龙11、MXD尼龙、无定形尼龙、共聚尼龙中的任1种以上。
[7]一种包含[3]~[6]中任一项所述的叠层体的膜。
[8]一种由[7]所述的膜得到的袋。
[9]一种包含[3]~[6]中任一项所述的叠层体的包装容器。
发明效果
本发明的粘接性树脂组合物对于乙烯-乙烯醇共聚物等阻气性树脂具有优异的粘接力。因此,在包含含有上述粘接性树脂组合物的粘接层和与该粘接层直接相接的阻气性树脂层的叠层体中,即使是为了使阻气性树脂层柔软化而添加添加剂的情况等时,由于上述两层牢固粘接,上述两层间也不易发生剥离。因此,上述叠层体能够有效地用作具有高阻气性的包装和容器等。
具体实施方式
<粘接性树脂组合物>
本发明的粘接性树脂组合物含有包含利用不饱和羧酸或其衍生物进行接枝改性的乙烯系聚合物的乙烯系聚合物(A)。
作为上述乙烯系聚合物(A)的优选方式,乙烯系聚合物(A)含有下述的乙烯系聚合物(A1)和乙烯系聚合物(A2),该乙烯系聚合物(A1)和(A2)中的至少一者包含利用不饱和羧酸或其衍生物进行接枝改性的乙烯系聚合物。
(A1)密度为930~965kg/m3且基于ASTMD1238测得的温度190℃、2160g负荷下的熔体流动速率(MFR)为0.1~10g/10分钟的乙烯系聚合物。
(A2)密度为858~929kg/m3且基于ASTMD1238测得的温度190℃、2160g负荷下的熔体流动速率(MFR)为0.1~10g/10分钟的乙烯系聚合物。
乙烯系聚合物(A1)的密度为930~965kg/m3,优选为940~965kg/m3。通过使用这样范围的密度的乙烯系聚合物(A1),容易得到粘接性优异的粘接性树脂组合物。
乙烯系聚合物(A1)的基于ASTMD1238测得的190℃、2160g负荷下的熔体流动速率(MFR)为0.1~10g/10分钟,优选为0.2~8g/10分钟。关于上述MFR小于0.1g/10分钟的聚合物,有时所得到的粘接性树脂组合物的挤出成型变得困难,存在压力上升而超过成型设备的极限压力的担忧。另一方面,关于MFR超过10g/10分钟的聚合物,将所得到的粘接性树脂组合物成型时,成型品的厚度的均匀性容易变得不良,还有分子量过低、叠层体的抗冲击强度等下降的担忧。
乙烯系聚合物(A2)的密度为858~929kg/m3,优选为865~925kg/m3。通过使用这样范围的密度的乙烯系聚合物(A2),容易得到粘接性优异的粘接性树脂组合物。
乙烯系聚合物(A2)的基于ASTMD1238测得的190℃、2160g负荷下的熔体流动速率(MFR)为0.1~10g/10分钟,优选为0.5~7g/10分钟。关于上述MFR小于0.1g/10分钟的聚合物,有时所得到的粘接性树脂组合物的挤出成型变得困难,存在压力上升而超过成型设备的极限压力的担忧。另一方面,关于MFR超过10g/10分钟的聚合物,将所得到的粘接性树脂组合物成型时,成型品的厚度的均匀性容易变得不良,还有分子量过低、叠层体的抗冲击强度等下降的担忧。
上述乙烯系聚合物(A1)和(A2)中的至少一者包含利用不饱和羧酸或其衍生物进行接枝改性的乙烯系聚合物。即,可以列举乙烯系聚合物(A1)包含改性乙烯系聚合物而乙烯系聚合物(A2)不含改性乙烯系聚合物的方式、乙烯系聚合物(A1)不含改性乙烯系聚合物而乙烯系聚合物(A2)包含改性乙烯系聚合物的方式、以及乙烯系聚合物(A1)和乙烯系聚合物(A2)都包含改性乙烯系聚合物的方式。
乙烯系聚合物(A1)或(A2)包含改性乙烯系聚合物时,乙烯系聚合物(A1)和(A2)各自的不饱和羧酸或其衍生物的接枝量通常为0.01~10质量%,优选为0.02~5质量%的范围。接枝量低于0.01质量%时,粘接力可能不充分;高于10质量%时,容易发生交联反应,所得到的改性乙烯系聚合物的品质难以稳定。
作为上述不饱和羧酸或其衍生物,例如可以列举丙烯酸、马来酸、富马酸、四氢邻苯二甲酸、衣康酸、柠康酸、巴豆酸、异巴豆酸、纳迪克酸(内顺-双环[2.2.1]庚-5-烯-二羧酸)等不饱和羧酸;或其衍生物、例如酰卤、酰胺酰亚胺、酸酐、酯等。作为这样的衍生物的具体例,例如可以列举马来酰氯、马来酰亚胺、马来酸酐、柠康酸酐、马来酸单甲酯、马来酸二甲酯、马来酸缩水甘油酯等。这些中,优选不饱和二羧酸及其酸酐,特别优选马来酸、纳迪克酸和它们的酸酐。
上述改性乙烯系聚合物可以利用各种公知的方法进行制造。例如可以采用:将乙烯系聚合物溶解在有机溶剂中,接着向所得到的溶液中添加不饱和羧酸或其衍生物和根据需要的有机过氧化物等自由基引发剂,通常以60~350℃、优选80~190℃的温度使其反应0.5~15小时、优选1~10小时的方法;或者使用挤出机等,在无溶剂下添加乙烯系聚合物、不饱和羧酸或其衍生物和根据需要的有机过氧化物等自由基引发剂,通常在乙烯系聚合物的熔点以上、优选120~350℃使其反应0.5~10分钟的方法。
乙烯系聚合物(A1)和乙烯系聚合物(A2)所含的不是改性乙烯系聚合物的非改性的乙烯系聚合物和改性乙烯系聚合物的改性前的乙烯系聚合物为乙烯的均聚物或乙烯与α-烯烃的共聚物。作为上述α-烯烃,可以列举碳原子数3以上、优选3~10的α-烯烃,具体可以列举丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、1-癸烯、4-甲基-1-戊烯和它们的2种以上的组合等。只要所得到的密度处于上述范围内,α-烯烃的共聚量就没有特别限定,通常为10摩尔%以下。只要所得到的改性乙烯系聚合物的密度处于上述范围内,改性前的乙烯系聚合物的密度就没有特别限定。
改性前的乙烯系聚合物可以利用公知的方法、例如高压法或者使用了齐格勒型的Ti系催化剂、Co系催化剂或茂金属系催化剂等的低压法进行制造。
关于乙烯系聚合物(A)中的乙烯系聚合物(A1)和乙烯系聚合物(A2)的含有比率,将乙烯系聚合物(A1)和乙烯系聚合物(A2)的合计设为100重量%,优选乙烯系聚合物(A1)为20~40质量%,乙烯系聚合物(A2)为60~80质量%,更优选乙烯系聚合物(A1)为23~37质量%,乙烯系聚合物(A2)为63~77质量%。乙烯系聚合物(A1)和乙烯系聚合物(A2)的含有比率为上述范围内时,能够更强地显现粘接性树脂组合物的粘接力。
乙烯系聚合物(A1)和乙烯系聚合物(A2)各自可以单独包含1种乙烯系聚合物,也可以包含2种以上的乙烯系聚合物。
乙烯系聚合物(A1)包含2种以上的乙烯系聚合物时,该2种以上的乙烯系聚合物分别满足关于上述乙烯系聚合物(A1)所述的密度和熔体流动速率的条件。
乙烯系聚合物(A2)包含2种以上的乙烯系聚合物时,该2种以上的乙烯系聚合物也分别满足关于上述乙烯系聚合物(A2)所述的密度和熔体流动速率的条件。
本发明的粘接性树脂组合物满足下述的条件(1)~(4)。
(1)基于ASTMD1238测得的温度190℃、2160g负荷下的熔体流动速率(MFR)为0.1~3g/10分钟,优选为0.5~2g/10分钟。通过熔体流动速率处于上述范围内,成为成型性良好的粘接性树脂组合物。
(2)密度为910~930kg/m3,优选为913~927kg/m3,更优选为914~925kg/m3,进一步优选为915~920kg/m3。密度小于910kg/m3的粘接性树脂组合物例如用于容器等时,机械强度可能下降,还有在80℃以上的高温下的层间粘接力下降的倾向。密度超过930kg/m3的粘接性树脂组合物例如用于与乙烯-乙烯醇共聚物等的叠层体时,层间粘接力容易不稳定,有叠层体的低温抗跌落抗冲击强度下降的倾向。
(3)在结晶洗脱分级色谱(CEF)测定中,在50℃以下的洗脱成分的比率为20质量%以上,优选为23质量%以上。在50℃以下的洗脱成分的比率优选为45质量%以下,更优选为40质量%以下。
(4)在结晶洗脱分级色谱(CEF)测定中,在90℃以上的洗脱成分的比率为25质量%以上,优选为28质量%以上。在90℃以上的洗脱成分的比率优选为45质量%以下,更优选为40质量%以下。
通过满足关于结晶洗脱分级色谱测定的上述条件(3)和(4),能够更强地显现粘接性树脂组合物的粘接力。如果是本领域技术人员,能够适当调整结晶洗脱分级色谱测定中的上述洗脱成分的比率。
本发明的粘接性树脂组合物可以利用各种公知的方法进行调制,例如利用亨舍尔混合机、转鼓掺混机、V-掺混机等将乙烯系聚合物(A1)和乙烯系聚合物(A2)在上述的比率范围内干混的方法;干混后利用单螺杆挤出机、多螺杆挤出机、班伯里混合机等进行熔融混炼的方法;和在溶剂的存在下进行搅拌混合的方法等。
在不损害本发明的目的的范围内,本发明的粘接性树脂组合物可以根据需要含有常用的抗氧化剂、耐候稳定剂、抗静电剂、防雾剂、防粘连剂、滑剂、成核剂、颜料等添加剂或其他的聚合物、橡胶等。
<叠层体>
本发明的叠层体叠层有:含有乙烯系聚合物的层(I);含有上述粘接性树脂组合物的粘接层(II);以及含有乙烯-乙烯醇共聚物的层(III)和/或含有聚酰胺树脂的层(IV),并且上述层(II)与层(III)和层(IV)中的至少一者直接相接。
本发明的叠层体还可以在含有乙烯系聚合物的层(I)与粘接层(II)之间存在回收料层(V)。回收料层(V)是包含将成型叠层体时产生的毛刺(burr)部分(不要部分)、叠层体的回收品(废品)、成型时产生的不良品等粉碎、或者根据需要利用挤出机等将该粉碎物熔融混炼而得到的物料(回收料)的层。回收料层(V)不一定只包含上述回收品,也可以在回收料层(V)中掺混例如用于层(I)的乙烯系聚合物,从而提高机械物性。
在不损害本发明的目的的范围内,构成本发明的叠层体的上述各层中可以配合填充剂、稳定剂、滑剂、抗静电剂、阻燃剂、发泡剂等自身公知的添加剂。
层(I)所含的乙烯系聚合物为乙烯的均聚物或乙烯与α-烯烃的无规共聚物。只要乙烯系聚合物的密度处于下述范围内,α-烯烃的共聚量就没有特别限定,通常优选为10摩尔%以下,更优选为5摩尔%以下。作为α-烯烃,优选碳原子数3~10的α-烯烃,具体而言,例如可以列举丙烯、1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯、1-癸烯等。
上述乙烯系聚合物的熔体流动速率(MFR)〔ASTMD1238(温度:190℃、负荷:2160g负荷)〕优选为0.01~5.0g/10分钟、更优选为0.05~4g/10分钟的范围。上述乙烯系聚合物的密度优选为940~980kg/m3、更优选为950~970kg/m3的范围。使用MFR大于上述范围的乙烯系聚合物时,存在形成叠层体时的抗冲击强度可能不充分的担忧。另一方面,MFR小于上述范围的乙烯系聚合物有挤出成型困难的倾向。使用密度低于上述范围的乙烯系聚合物时,存在所得到的叠层体的透过性可能变差的担忧。
层(III)和层(IV)为阻气性树脂层。
层(III)所含的乙烯-乙烯醇共聚物(以下,也称为EVOH。)优选将乙烯含有率20~30摩尔%、优选22~29摩尔%的乙烯-乙酸乙烯酯共聚物皂化而得到。皂化度没有特别限制,例如为90~100%,优选为95~100%。乙烯含有率小于20摩尔%的皂化物的熔点与分解温度接近,存在可能难以微细地分散在乙烯系聚合物中的担忧。另外,乙烯含有率过大时,存在阻隔性下降而无法实现本发明的目的的担忧。
层(III)所含的EVOH可以为还含有苯乙烯系弹性体10~40质量%的聚合物。层(III)通过含有苯乙烯系弹性体,能够保持优异的阻气性,并且赋予膜柔软性。
作为上述苯乙烯系弹性体的具体例,可以列举苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)、SBS的氢化嵌段共聚物(SEBS)、SIS的氢化嵌段共聚物(SEPS)、使SBS的丁二烯嵌段的乙烯基结合部分氢化而得到的嵌段共聚物(SBBS)、苯乙烯-异丁烯-苯乙烯三嵌段共聚物(SIBS)、苯乙烯-乙烯-丁烯-结晶聚烯烃嵌段共聚物(SEBC)等。这些中,优选使用热稳定性、耐候性优异的SEBS。SEBS的聚丁二烯嵌段通过氢化而形成乙烯-丁烯的共聚物嵌段。
作为层(IV)所含的聚酰胺,例如可以例示尼龙6、尼龙66、尼龙610、尼龙12、尼龙11、MXD尼龙、无定形尼龙、共聚尼龙等。
作为本发明的叠层体的层构成,例如可以列举含有乙烯系聚合物的层(I)(以下,简称为“PE层(I)”。)/含有粘接性树脂组合物的粘接层(II)(以下,简称为“粘接层(II)”。)/含有乙烯-乙烯醇共聚物的层(以下,简称为“EVOH层”。)(III)和PE层(I)/粘接层(II)/含有聚酰胺树脂的层(以下,简称为“NY层”。)(IV)的3层结构。
除此以外,还可以形成:
PE层(I)/回收料层(V)/粘接层(II)/EVOH层(III)、PE层(I)/回收料层(V)/粘接层(II)/NY层(IV)、PE层(I)/粘接层(II)/EVOH层(III)/粘接层(II)、PE层(I)/粘接层(II)/NY层(IV)/粘接层(II)的4层结构;
PE层(I)/回收料层(V)/粘接层(II)/EVOH层(III)/粘接层(II)、PE层(I)/回收料层(V)/粘接层(II)/NY层(IV)/粘接层(II)、PE层(I)/粘接层(II)/EVOH层(III)/粘接层(II)/PE层(I)、PE层(I)/粘接层(II)/NY层(IV)/粘接层(II)/PE层(I)的5层结构;
PE层(I)/回收料层(V)/粘接层(II)/EVOH层(III)/粘接层(II)/PE层(I)、PE层(I)/回收料层(V)/粘接层(II)/NY层(IV)/粘接层(II)/PE层(I)的6层结构;
PE层(I)/回收料层(V)/粘接层(II)/EVOH层(III)/粘接层(II)/回收料层(V)/PE层(I)、PE层(I)/回收料层(V)/粘接层(II)/NY层(IV)/粘接层(II)/回收料层(V)/PE层(I)的7层结构等层结构。
本发明的叠层体例如可以利用共挤出膜成型、片材成型、涂布、吹塑、挤出层压等公知的成型方法进行制造。
本发明的叠层体,其阻气性优异,并显示优异的层间粘接力和耐久性、耐热粘接性。本发明的叠层体由于具有这样的特性,所以能够用于各种用途。例如,可以利用本发明的叠层体制造包含该叠层体的膜,进而可以由该膜得到袋。另外,还可以由本发明的叠层体制造包含该叠层体的包装容器。
实施例
接着,列举实施例对本发明进行更具体的说明,但只要不超出其宗旨,本发明就不受这些实施例任何限制。
其中,实施例和比较例中的物性测定按照以下的测定方法进行。
(1)熔体流动速率(MFR)(g/10分钟)
熔体流动速率按照ASTMD1238以温度190℃、2160g负荷进行测定。
(2)密度(kg/m3)
密度按照ASTMD1505进行测定。
(3)在50℃以下的洗脱成分的比率(%)和在90℃以上的洗脱成分的比率(%)
在50℃以下的洗脱成分的比率和在90℃以上的洗脱成分的比率利用结晶洗脱分级色谱(CEF)进行测定,利用在50℃以下洗脱的成分的峰面积相对于全部峰面积的比率和在90℃以上洗脱的成分的峰面积相对于全部峰面积的比率求得。
(4)粘接强度(N/15mm)
关于叠层体的初始粘接强度,从叠层体的侧面侧切出15mm宽的样品,在23℃的恒温槽内测定内层侧的粘接层(II)与含有乙烯-乙烯醇共聚物的层(III)之间的粘接强度。剥离试验的测定方法为T-剥离法,剥离速度为300mm/分钟。将该测定进行5次,将所得到的数值的平均作为该叠层体的粘接强度。
(5)熔点(℃)
熔点利用DSC进行测定。具体而言,将试样5-10mg左右填入专用铝制皿中,以500℃/min从30℃升温至200℃,在200℃保持10分钟后,以10℃/min从200℃降温至30℃,在30℃再保持1分钟,接着以10℃/min进行升温,利用此时的吸热曲线求出熔点。
将实施例和比较例中所使用的作为乙烯系聚合物的PE-0、PE-1、PE-2、PE-3、PE-4、PE-5(以下,也分别记为乙烯系聚合物(PE-0)~(PE-5))示于表1。其中,这些乙烯系聚合物均利用通常方法进行聚合而调制。另外,在表1中,MAH量是指作为不饱和羧酸或其衍生物使用的马来酸酐的接枝量,共聚单体含量是指来自共聚单体的结构单元占构成乙烯系聚合物的全部结构单元的摩尔比。
[表1]
〔实施例1〕
配合作为乙烯系聚合物(A1)的乙烯系聚合物(PE-0)9质量%和乙烯系聚合物(PE-5)26质量%与作为乙烯系聚合物(A2)的乙烯系聚合物(PE-2)35质量%和乙烯系聚合物(PE-3)30质量%,将所得到的混合物利用单螺杆挤出机进行熔融混合,得到粘接性树脂组合物(1)。所得到的粘接性树脂组合物(1)的密度为0.919g/cm3,基于ASTMD1238的190℃、2.16kg负荷下的MFR为0.8g/10分钟。
使用粘接性树脂组合物(1),在下述的成型条件下利用共挤出成型制造由5层构成的叠层体(膜)。利用上述方法测定所得到的5层膜的EVOH层(III)与包含粘接性树脂组合物(1)的粘接层(II)的层间粘接强度(剥离强度)。将结果示于表2。
<叠层体的成型条件>
层结构:
LLDPE层(I)/接着层(II)/EVOH层(III)/接着层(II)/LLDPE层(I)
层的厚度:LLDPE层(I) 350μm
粘接层(II) 20μm
EVOH层(III) 20μm
T-模成型机:
成型速度:1.5m/分钟
作为LLDPE层(I),使用由下述的LLDPE构成的层。
作为EVOH层(III),使用由下述的EVOH1或EVOH2构成的层,制造含有由EVOH1构成的EVOH层(III)的叠层体和含有由EVOH2构成的EVOH层(III)的叠层体。
EVOH1:乙烯-乙烯醇共聚物(乙烯含量27摩尔%、含有SEBS25质量%、MFR1.3g/10分钟)
EVOH2:乙烯-乙烯醇共聚物(乙烯含量44摩尔%、MFR1.7g/10分钟)
LLDPE:直链状低密度聚乙烯(普瑞曼聚合物株式会社制造的Ultzex2021L)
〔实施例2、比较例1~4〕
对于实施例2、比较例1~4,如表2所示那样地改变配方,除此以外,按照与实施例1相同的方法调制粘接性树脂组合物。使用所得到的粘接性树脂组合物,与实施例1同样制造叠层体,测定其粘接强度。将结果示于表2。
[表2]
如表2所示,在CEF测定中,90℃以上的洗脱量为25%以上且50℃以下的洗脱量为20%以上的实施例1~实施例3中所得到的叠层体对于EVOH1显示良好的粘接强度。另一方面,在CEF测定中,90℃以上的洗脱量小于25%或50℃以下的洗脱量小于20%的比较例1~5对于EVOH1的粘接强度低。
Claims (9)
1.一种粘接性树脂组合物,其特征在于:
含有包含利用不饱和羧酸或其衍生物进行接枝改性的乙烯系聚合物的乙烯系聚合物(A),并且该组合物满足下述的条件(1)~(4):
(1)基于ASTMD1238测得的温度190℃、2160g负荷下的熔体流动速率(MFR)为0.1~3g/10分钟;
(2)密度为910~930kg/m3;
(3)在结晶洗脱分级色谱测定中,在50℃以下的洗脱成分的比率为20质量%以上;
(4)在结晶洗脱分级色谱测定中,在90℃以上的洗脱成分的比率为25质量%以上。
2.如权利要求1所述的粘接性树脂组合物,其特征在于:
所述乙烯系聚合物(A)含有下述的乙烯系聚合物(A1)20~40质量%和乙烯系聚合物(A2)60~80质量%,其中,将乙烯系聚合物(A1)和乙烯系聚合物(A2)的合计设为100质量%,所述乙烯系聚合物(A1)和乙烯系聚合物(A2)中的至少一者包含利用不饱和羧酸或其衍生物进行接枝改性的乙烯系聚合物,
(A1)密度为930~965kg/m3且基于ASTMD1238测得的温度190℃、2160g负荷下的熔体流动速率(MFR)为0.1~10g/10分钟的乙烯系聚合物,
(A2)密度为858~929kg/m3且基于ASTMD1238测得的温度190℃、2160g负荷下的熔体流动速率(MFR)为0.1~10g/10分钟的乙烯系聚合物。
3.一种叠层体,其特征在于:
叠层有:含有乙烯系聚合物的层(I);含有权利要求1或2所述的粘接性树脂组合物的粘接层(II);以及含有乙烯-乙烯醇共聚物的层(III)和/或含有聚酰胺树脂的层(IV),
并且所述层(II)与层(III)和层(IV)中的至少一者直接相接。
4.如权利要求3所述的叠层体,其特征在于:
所述乙烯-乙烯醇共聚物为将源自乙烯的结构单元的含有率为20~30摩尔%的乙烯-乙酸乙烯酯共聚物皂化而得到的聚合物。
5.如权利要求3所述的叠层体,其特征在于:
所述乙烯-乙烯醇共聚物为还含有苯乙烯系弹性体10~40质量%的聚合物。
6.如权利要求3~5中任一项所述的叠层体,其特征在于:
所述聚酰胺树脂含有尼龙6、尼龙66、尼龙610、尼龙12、尼龙11、MXD尼龙、无定形尼龙、共聚尼龙中的任1种以上。
7.一种包含权利要求3~6中任一项所述的叠层体的膜。
8.一种由权利要求7所述的膜得到的袋。
9.一种包含权利要求3~6中任一项所述的叠层体的包装容器。
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JP5797909B2 (ja) | 2010-03-02 | 2015-10-21 | 日本合成化学工業株式会社 | 樹脂組成物並びにこれを用いた成形品及び多層構造体 |
US10155889B2 (en) | 2014-08-21 | 2018-12-18 | Dow Global Technologies Llc | Hot melt adhesive composition including a block composite compatibilizer |
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2019
- 2019-04-05 KR KR1020207030348A patent/KR20200135464A/ko not_active Application Discontinuation
- 2019-04-05 WO PCT/JP2019/015117 patent/WO2019208169A1/ja unknown
- 2019-04-05 CN CN201980027443.0A patent/CN112004902A/zh active Pending
- 2019-04-05 JP JP2020516182A patent/JP7105301B2/ja active Active
- 2019-04-05 US US17/046,626 patent/US11292945B2/en active Active
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JPS61162539A (ja) * | 1985-01-08 | 1986-07-23 | Mitsui Petrochem Ind Ltd | 接着用変性ポリオレフイン組成物 |
CN1526761A (zh) * | 1995-09-12 | 2004-09-08 | ������ѧ��ʽ���� | 粘合的乙烯共聚物树脂组合物和含它的层压材料 |
CN1460117A (zh) * | 2001-03-28 | 2003-12-03 | 日本聚烯烃株式会社 | 粘接性树脂组合物及用该组合物的多层层压结构体 |
CN103443231A (zh) * | 2011-03-25 | 2013-12-11 | 三井化学株式会社 | 粘合性树脂组合物及使用其的多层结构体 |
Also Published As
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US11292945B2 (en) | 2022-04-05 |
WO2019208169A1 (ja) | 2019-10-31 |
KR20200135464A (ko) | 2020-12-02 |
JPWO2019208169A1 (ja) | 2021-05-13 |
US20210108112A1 (en) | 2021-04-15 |
EP3786250A1 (en) | 2021-03-03 |
JP7105301B2 (ja) | 2022-07-22 |
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