CN114126867A - 阻气层叠体和使用了该阻气层叠体的包装材料 - Google Patents
阻气层叠体和使用了该阻气层叠体的包装材料 Download PDFInfo
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- CN114126867A CN114126867A CN202080051696.4A CN202080051696A CN114126867A CN 114126867 A CN114126867 A CN 114126867A CN 202080051696 A CN202080051696 A CN 202080051696A CN 114126867 A CN114126867 A CN 114126867A
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- layer
- gas barrier
- polyvinyl alcohol
- barrier laminate
- alcohol resin
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract
本公开涉及的阻气层叠体具有层叠结构,该层叠结构依次具备聚丙烯类基材层、第1聚乙烯醇类树脂层、以及金属氧化物层,第1聚乙烯醇类树脂层的每单位面积的质量为0.5~2.5g/m2。本公开涉及的包装材料具有:上述阻气层叠体;以及设置在阻气层叠体的表面上的聚丙烯类密封剂层,以该包装材料的总质量为基准,聚丙烯类基材层和聚丙烯类密封剂层的合计质量比为85质量%以上。
Description
技术领域
本公开涉及阻气层叠体和使用了该阻气层叠体的包装材料。
背景技术
已知有具备:作为基膜的耐热性和韧性优异的双轴拉伸PET(聚对苯二甲酸乙二醇酯)膜、以及作为密封剂层的聚乙烯或聚丙烯等聚烯烃膜的层叠体(软包装材料)(例如,专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开2017-178357号公报
发明内容
发明所要解决的课题
近年来,由于海洋塑料垃圾问题等引发的环保意识的不断提高,要求塑料材料的分类回收和再资源化的更高效化。即,即使是以往通过组合各种不同的材料来实现高性能化的软包装材料,也开始要求单一材料化。
本公开提供了一种用于实现包装材料的优异的可再利用性并且具有优异的阻气性的阻气层叠体。本公开提供了一种使用了该阻气层叠体的包装材料。
用于解决课题的方案
本公开的一个方面涉及的阻气层叠体具有层叠结构,该层叠结构依次具备聚丙烯类基材层、第1聚乙烯醇类树脂层、以及金属氧化物层,第1聚乙烯醇类树脂层的每单位面积的质量为0.5~2.5g/m2。根据该阻气层叠体,第1聚乙烯醇类树脂层介于聚丙烯类基材层与金属氧化物层之间,因此即使聚丙烯类基材层的表面不一定高度平滑,也可以实现优异的阻气性。从实现更优异的阻气性的观点来看,第1聚乙烯醇类树脂层的表面粗糙度Sa优选为0.2μm以下、更优选为0.1μm以下。
本发明人致力于开发这样的阻气层叠体:其与密封剂层并用而构成包装材料,并且可以实现获得可再利用性优异的单一材料的包装材料。为了实现含有广泛用作密封剂膜的未拉伸聚丙烯膜(CPP膜)的包装材料的单一材料化,需要使用聚丙烯类膜(PP类膜)作为阻气层叠体的基材层,但是考虑到包装材料的耐热性,这并不意味着任何种类的PP类膜都是可以的,使用与其他PP类膜相比具有更优异的耐热性的丙烯的单聚物膜是有用的。有时会在容纳有食品等的状态下对包装材料进行煮沸处理或蒸煮处理等加热杀菌处理,因此需要具有耐热性。
但是,根据本发明人的评价试验,丙烯的单聚物膜具有其表面容易成为叶脉状的缺点,即使在丙烯的单聚物膜的表面上直接形成金属氧化物层(阻气层),也无法实现充分的阻挡性。因此,通过使聚乙烯醇类树脂层介于作为基材层的丙烯的单聚物膜与金属氧化物层之间,开发了具有优异的阻气性并且对于得到单一材料的包装材料有用的阻气层叠体。
从实现阻气层叠体的优异的耐热性的观点来看,如上所述,聚丙烯类基材层优选为丙烯的单聚物层。
本公开涉及的上述阻气层叠体可以进一步具有:与第1聚乙烯醇类树脂层一起夹着金属氧化物层的第2聚乙烯醇类树脂层。通过采用由第1和第2聚乙烯醇类树脂层夹着金属氧化物层的构成,可以实现更优异的阻气性。从保持与金属氧化物层的密合性和阻气性的观点来看,第2聚乙烯醇类树脂层可以含有硅烷化合物。硅烷化合物相对于第2聚乙烯醇类树脂层的质量的质量比例如为0.05~0.95。
本公开的一个方面涉及的包装材料具备:上述阻气层叠体;以及设置在阻气层叠体的表面上的聚丙烯类密封剂层,以该包装材料的总质量为基准,聚丙烯类基材层和聚丙烯类密封剂层的合计质量比为85质量%以上,可以为90质量%以上或95质量%以上,这取决于聚丙烯类密封剂层的厚度。根据该包装材料,通过并用上述阻气层叠体和聚丙烯类密封剂层,可以实现包装材料的单一材料化。需要说明的是,在本公开中,单一材料的包装材料是指:特定材料(聚丙烯类材料)的质量比率为85质量%以上(优选为90质量%以上或95质量%以上)的包装材料。
发明效果
根据本公开,可以提供一种用于实现包装材料的优异的可再利用性并且具有优异的阻气性的阻气层叠体。根据本公开,可以提供一种使用了该阻气层叠体的包装材料。
附图说明
[图1]图1为示意性地示出本公开涉及的阻气层叠体的一个实施方式的剖面图。
[图2]图2(a)和图2(b)为分别示意性地示出图1所示的阻气层叠体的变形例的剖面图。
[图3]图3为示意性地示出使用了图1所示的阻气层叠体的包装材料的剖面图。
[图4]图4为示意性地示出本公开涉及的阻气层叠体的其他实施方式的剖面图。
[图5]图5为示意性地示出本公开涉及的包装材料的其他实施方式的剖面图。
具体实施方式
以下,根据情况参照附图对本公开的实施方式进行详细的说明。需要说明的是,在附图中,对相同或相当的部分标注相同的符号,并省略重复的说明。此外,附图的尺寸比例不限于图示的比例。
<阻气层叠体>
图1为示出本实施方式涉及的阻气层叠体的示意性剖面图。图1所示的阻气层叠体10具有层叠结构,该层叠结构依次具备基材层1、第1聚乙烯醇类树脂层3a、金属氧化物层5、以及第2聚乙烯醇类树脂层3b。
(基材层)
基材层1由聚丙烯类树脂构成。作为聚丙烯类树脂,例如可列举出:丙烯的均聚物、无规共聚物以及嵌段共聚物。在要求基材层1具有耐热性的情况下,聚丙烯类树脂优选为丙烯的均聚物。但是,如上所述,丙烯的均聚物膜具有其表面容易形成叶脉状的缺点。叶脉状的膜表面的表面粗糙度Sa例如超过0.2μm、可以为0.21~0.5μm。
需要说明的是,在本公开中,各层的表面粗糙度Sa是指:使用三维非接触表面形状测量***(Vertscan R3300h Lite、“株式会社菱化システム”制),在以下条件下测定的值。
·测定模式:相位
·扫描速度:4μm/秒
·扫描范围:10/-20μm
·扫描次数:1次
·插值:完全插值
·面补正:4次
·镜筒镜头:1倍
·物镜:5倍
通过使用丙烯的均聚物膜作为基材层1,可以使阻气层叠体10耐受煮沸处理或蒸煮处理等加热杀菌处理。需要说明的是,煮沸处理的温度为60~100℃左右,蒸煮处理的温度为105~140℃左右。
构成基材层1的膜可以是拉伸膜,也可以是未拉伸膜。但是,从耐冲击性、耐热性、耐水性、尺寸稳定性等观点来看,构成基材层1的膜可以是拉伸膜。作为拉伸方法没有特别地限定,只要能够提供尺寸稳定的膜,可以使用膨胀拉伸、单轴拉伸或双轴拉伸等任何方法。
基材层1的厚度没有特别地限定,但是从得到优异的耐冲击性和优异的阻气性的观点来看,可以设为10~100μm、可以为15~30μm。在不损害阻挡性能的范围内,可以对构成基材层1的膜的层叠面F1进行电晕处理、等离子体处理、火焰处理等各种前处理,或者也可以设置用于提高密合性的涂层1a(密合层)(参照图2(a))。此外,也可以在基材层1的外表面F2上设置共聚物层1b。作为构成聚合物层1c的树脂的具体例子,可列举出:丙烯与其他单体的共聚物。其他单体例如为乙烯和丁烯中的至少一者。
根据需要,构成基材层1的聚丙烯类树脂可以含有防静电剂、紫外线吸收剂、增塑剂、滑剂等添加剂。需要说明的是,从高度实现阻气层叠体10和使用了该阻气层叠体10的包装材料50的单一材料化的观点来看,基材层1中的聚丙烯类树脂的质量比优选为90质量%以上、更优选为95质量%以上。
(第1聚乙烯醇类树脂层)
作为构成第1聚乙烯醇类树脂层3a的树脂,只要具有将乙烯基酯单元皂化而成的乙烯醇单元即可,例如可列举出:聚乙烯醇(PVA)、乙烯-乙烯醇共聚物(EVOH)。从耐热性和阻气性的观点来看,可以优选使用EVOH。
作为PVA,例如可列举出:将乙酸乙烯酯、甲酸乙烯酯、丙酸乙烯酯、戊酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、新戊酸乙烯酯、新癸酸乙烯酯等乙烯基酯均聚、接着进行皂化而得的树脂。
PVA也可以是共聚改性或后改性的改性PVA。共聚改性PVA例如可以通过使乙烯基酯与能够与乙烯基酯共聚的不饱和单体共聚后进行皂化来得到。后改性的PVA是通过在聚合催化剂的存在下,使乙烯基酯皂化而得到的PVA与不饱和单体共聚而得到的。从表现出充分的阻气性的观点来看,改性PVA中的改性量可以小于50摩尔%,此外,从得到改性效果的观点来看,可以设为10摩尔%以上。
作为上述不饱和单体,例如可列举出:乙烯、丙烯、异丁烯、α-辛烯、α-十二烯、α-十八烯等烯烃;3-丁烯-1-醇、4-戊炔-1-醇、5-己烯-1-醇等含羟基的α-烯烃;丙烯酸、甲基丙烯酸、巴豆酸、马来酸、马来酸酐、衣康酸、十一烯酸等不饱和酸;丙烯腈、甲基丙烯腈等腈;双丙酮丙烯酰胺、丙烯酰胺、甲基丙烯酰胺等酰胺;乙烯磺酸、烯丙基磺酸、甲基烯丙基磺酸等烯烃磺酸;烷基乙烯基醚、二甲基烯丙基乙烯基酮、N-乙烯基吡咯烷酮、氯乙烯、碳酸乙烯基亚乙酯、2,2-二烷基-4-乙烯基-1,3-二氧戊环、甘油单烯丙基醚、3,4-二乙酰氧基-1-丁烯等乙烯基化合物;偏二氯乙烯、1,4-二乙酰氧基-2-丁烯、碳酸亚乙烯酯、聚氧丙烯、聚氧丙烯乙烯基胺等。从阻气性的观点来看,作为不饱和单体可以是烯烃,特别是可以是乙烯。
作为聚合催化剂,可列举出:偶氮二异丁腈、过氧化苯甲酰、过氧化月桂酰等自由基聚合催化剂。聚合方法没有特别地限定,可以采用本体聚合、乳液聚合、溶剂聚合等。
PVA的聚合度优选为300~3000。当聚合度小于300时,阻挡性容易降低;此外当超过3000时,粘度过高,涂布适性容易降低。PVA的皂化度优选为80摩尔%以上、更优选为90摩尔%以上、进一步优选为99摩尔%以上。此外,PVA的皂化度可以是100摩尔%以下、也可以是99.9摩尔%以下。PVA的聚合度和皂化度可以按照JIS K 6726(1994)所记载的方法进行测定。
EVOH通常是通过将乙烯与乙酸乙烯酯、甲酸乙烯酯、丙酸乙烯酯、戊酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、新戊酸乙烯酯、新癸酸乙烯酯等酸性乙烯酯的共聚物皂化而得到的。
EVOH的聚合度优选为300~3000。当聚合度小于300时,阻挡性容易降低,此外当超过3000时,粘度过高,涂布适性容易降低。EVOH的乙烯基酯成分的皂化度优选为80摩尔%以上、更优选为90摩尔%以上、进一步优选为99摩尔%以上。此外,EVOH的皂化度可以为100摩尔%以下、也可以为99.9摩尔%以下。EVOH的皂化度是通过进行核磁共振(1H-NMR)测定,并根据乙烯基酯结构中所含的氢原子的峰面积和乙烯醇结构中所含的氢原子的峰面积求出的。
EVOH的乙烯单元含量例如为10摩尔%以上、更优选为15摩尔%以上、进一步优选为20摩尔%以上、特别优选为25摩尔%以上。此外,EVOH的乙烯单元含量优选为65摩尔%以下、更优选为55摩尔%以下、进一步优选为50摩尔%以下。当乙烯单元含量为10摩尔%以上时,可以良好地保持高湿度下的阻气性或尺寸稳定性。另一方面,当乙烯单元含量为65摩尔%以下时,可以提高阻气性。EVOH的乙烯单元含量可以通过NMR法求出。
可以使用碱或酸进行皂化,但是从皂化速度的观点来看,可以使用碱。作为碱,可列举出:氢氧化钠、氢氧化钾等碱金属氧化物、乙醇钠、乙醇钾、甲醇锂等碱金属醇盐。
第1聚乙烯醇类树脂层3a的每单位面积的质量为0.5~2.5g/m2、可以为0.5~2.0g/m2或0.5~1.5g/m2。当该质量为0.5g/m2以上时,即使基材层1的层叠面F1的平滑性不足,也可以充分平滑地形成第1聚乙烯醇类树脂层3a的表面F3,从而可以在表面F3上形成阻气性优异的金属氧化物层5。另一方面,当该质量为2.5g/m2以下时,在实现聚丙烯类树脂单一材料化和降低材料成本方面是有利的。需要说明的是,从与上述每单位面积的质量相同的观点来看,第1聚乙烯醇类树脂层3a的厚度例如为0.4~2.0μm、也可以为0.4~1.7μm或0.4~1.3μm。树脂层的厚度可以基于树脂层的每单位面积的质量和树脂的密度来计算。
第1聚乙烯醇类树脂层3a的表面F3的表面粗糙度Sa例如为0.2μm以下、也可以为0.01~0.1μm或0.02~0.1μm。由于表面F3的表面粗糙度Sa为0.2μm以下,因此可以在表面F3上形成阻气性优异的金属氧化物层5。另一方面,与小于0.01μm的情况相比,由于表面F3的表面粗糙度Sa为0.01μm以上,因此可以通过锚定效应而提高第1聚乙烯醇类树脂层3a与金属氧化物层5的密合性。
(金属氧化物层)
金属氧化物层5具有阻气性。作为金属氧化物,可列举出氧化硅(SiOx)和氧化铝(AlOx)等。通过采用这些金属氧化物,可以在抑制厚度的同时获得高阻气性。从加工时拉伸伸长性优异的观点来看,金属氧化物层5可以由氧化硅构成。
金属氧化物层5的厚度例如为5~100nm、可以为10~50nm或20~40nm。当金属氧化物层5的厚度为5nm以上时,可以获得充分的阻气性;另一方面,当为100nm以下时,可以抑制因金属氧化物层5的内部应力引起的变形而产生裂纹,从而可以保持优异的阻气性。
(第2聚乙烯醇类树脂层)
关于构成第2聚乙烯醇类树脂层3b的聚乙烯醇类树脂,可以参照对于第1聚乙烯醇类树脂层3a所描述的内容。
第2聚乙烯醇类树脂层3b可以含有硅烷化合物。作为硅烷化合物,可列举出:四甲氧基硅烷、四乙氧基硅烷等四烷氧基硅烷,环氧丙氧基丙基三甲氧基硅烷、丙烯酰氧基丙基三甲氧基硅烷等含有反应性基团的三烷氧基硅烷,六甲基二硅氮烷等硅氮烷等。作为硅烷化合物,也可以使用通常用作硅烷偶联剂的化合物、或具有硅氧烷键的聚硅氧烷化合物。
从与金属氧化物层的密合性和保持阻气性的观点来看,上述硅烷化合物相对于第2聚乙烯醇类树脂层3b的质量的质量比例如为0.05~0.95、可以为0.1~0.8或0.3~0.7。
第2聚乙烯醇类树脂层3b的厚度例如为0.1~1.0μm、可以为0.1~0.8μm或0.2~0.7μm。由于该厚度为0.1μm以上,因此可以实现优异的阻气性,并且可以长期充分地保持该阻气性。另一方面,该厚度为1.0μm以下则在实现聚丙烯类树脂单一材料化和降低材料成本方面是有利的。
<阻气层叠体的制造方法>
阻气层叠体10例如可以经由下述工序来制造:在基材层1上形成第1聚乙烯醇类树脂层3a的工序;在第1聚乙烯醇类树脂层3a上形成金属氧化物层5的工序;以及在金属氧化物层5上形成第2聚乙烯醇类树脂层3b的工序。
(形成第1聚乙烯醇类树脂层的工序)
在本工序中,可以使用含有聚乙烯醇类树脂和液体介质的涂布液。该涂布液例如可以通过将由合成得到的聚乙烯醇类树脂的粉末溶解在液体介质中而得到。作为液体介质,可列举出:水、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、各种二醇类、三羟甲基丙烷等多元醇类,乙二胺、二亚乙基三胺等胺类等。它们可以单独使用或将二种以上组合使用。从降低环境负荷等的观点来看,可以使用水作为液体介质。在这种情况下,通过将聚乙烯醇类树脂的粉末溶解在高温(例如80℃)的水中,可以得到涂布液。
从保持良好的涂布性的观点来看,涂布液中的聚乙烯醇类树脂(固体成分)的含量可以为3~20质量%。为了提高密合性,涂布液可以含有异氰酸酯或聚乙烯亚胺等添加剂。此外,涂布液也可以含有防腐剂、增塑剂(醇等)、表面活性剂等添加剂。
可以通过任意适当的方法,在基材层1上进行涂布液的涂布。涂布液的涂布例如可以通过凹版涂布机、浸涂机、逆向涂布机、线棒涂布机、模涂机等湿式成膜法来进行。涂布液的涂布温度和干燥温度没有特别地限定,例如可以设为50℃以上。
也可以通过挤出法在基材层1上形成第1聚乙烯醇类树脂层3a。在这种情况下,可以采用使用了T型模具的多层挤出。作为可以在挤出时使用的粘接剂,例如可列举出:使作为固化剂的具有2个官能团以上的芳香族类或脂肪族类异氰酸酯化合物作用在聚酯多元醇、聚醚多元醇、丙烯酸多元醇等主剂上的二液固化型的聚氨酯类粘接剂。通过将上述粘接成分涂布在基材层1上后干燥,可以在基材层1上预先形成粘接层。在使用聚氨酯类粘接剂的情况下,涂布后,例如在40℃老化4天以上,使主剂的羟基与固化剂的异氰酸酯基发生反应,从而可以牢固地粘接在一起。从粘接性、追随性、加工性等观点来看,粘接层的厚度可以设为1~50μm、也可以为3~20μm。
(形成金属氧化物层的工序)
金属氧化物层5例如可以通过真空成膜来形成。在真空成膜中,可以使用物理气相沉积法或化学气相沉积法。作为物理气相沉积法,可以列举出:真空蒸镀法、溅射法、离子镀法等,但是并不限于这些。作为化学气相沉积法,可以列举出:热CVD法、等离子体CVD法、光CVD法等,但是并不限于这些。
在上述真空成膜中,特别优选使用:电阻加热式真空蒸镀法、EB(电子束:ElectronBeam)加热式真空蒸镀法、感应加热式真空蒸镀法、溅射法、反应性溅射法、双磁控溅射法、等离子体化学气相沉积法(PECVD法)等。但是,如果考虑到生产率,目前真空蒸镀法是最好的。作为真空蒸镀法的加热手段,优选使用电子束加热法、电阻加热法、感应加热法中的任一种方法。
在溅射法的情况下,在作为阴极的靶中产生负电位梯度,Ar+离子接受电势能并与靶碰撞。这里,即使产生等离子体,但如果不产生负的自偏置电位也无法进行溅射。因此,MW(Micro Wave,微波)等离子体不会产生自偏置,因此不适合溅射。但是,在PECVD法中,利用等离子体中的气相反应进行化学反应、沉积和工艺,即使没有自偏置也可以生成膜,因此可以利用MW等离子体。
(形成第2聚乙烯醇类树脂层的工序)
本工序可以与形成第1聚乙烯醇类树脂层3a的工序同样地使用涂布液。关于涂布液,可以参照在形成第1聚乙烯醇类树脂层3a的工序的项目中所描述的内容。
用于形成第2聚乙烯醇类树脂层3b的涂布液可以含有硅烷化合物。以使得第2聚乙烯醇类树脂层3b中包含所期望量的硅烷化合物的方式调整涂布液中的硅烷化合物的含量即可。在涂布液中含有硅烷化合物的情况下,涂布液可以进一步含有酸催化剂、碱催化剂、光聚合引发剂等。
<包装材料>
图3所示的包装材料50具备:阻气层叠体10、以及设置在阻气层叠体10的内表面10F上的聚丙烯类密封剂层20。以包装材料50的总质量为基准,基材层1和聚丙烯类密封剂层20的合计质量比为85质量%以上(优选为90质量%以上或95质量%以上),包装材料50可以实现单一材料。
例如,使用粘接剂(未图示)将阻气层叠体10与聚丙烯类密封剂层20粘合在一起即可。作为粘接剂,例如可以使用含有直链状低密度聚乙烯(LLDPE)、聚氨酯、聚丙烯、乙烯-不饱和酯共聚树脂、或聚酯类共聚树脂等材料。粘接剂层的厚度例如为1~5μm左右即可。作为聚丙烯类密封剂层20的具体例子,例如可列举出未拉伸聚丙烯膜(CPP膜)。聚丙烯类密封剂层20的厚度例如为10~100μm。
以上,对本公开的实施方式进行了详细的说明,但是本发明不限于上述实施方式。例如,在上述实施方式中示例出了具有第2聚乙烯醇类树脂层3b的阻气层叠体10,但是根据阻气层叠体的用途,也可以不具备第2聚乙烯醇类树脂层3b(参照图4)。
在上述实施方式中,示例出了在阻气层叠体10的阻挡侧的表面上粘合有聚丙烯类密封剂层20的包装材料50,但是也可以将聚丙烯类密封剂层20粘合在阻气层叠体10的基材层1侧的表面上(参照图5)。图5所示的包装材料60具有如下构成:阻气层叠体10的阻挡侧与普通OPP膜8(印刷基材等)相面对,并且在阻气层叠体10的基材层1侧粘合有聚丙烯类密封剂层20。
实施例
以下,通过实施例对本公开进行更具体的说明,但是本发明不限于这些实施例。
准备了以下材料作为实施例和比较例中的材料。
(基材层)
·聚丙烯类树脂:丙烯的单聚物(单PP)
(聚乙烯醇类树脂层)
·EVOH:エバールL171B(“株式会社クラレ”制)
·PVA:ポバール60-98(“株式会社クラレ”制)
·TEOS:KBE04(“信越化学工業株式会社”制)
(密封剂层)
·聚丙烯类密封剂膜:トレファンZK207#60(CPP、厚度60μm、“東レ株式会社”)
(实施例1)
使用上述单PP来制作OPP膜(基材层),同时通过挤出法在OPP膜的表面上形成EVOH层(第1聚乙烯醇类树脂层)。EVOH层的每单位面积的质量为0.97g/m2。EVOH层的厚度为0.8μm,表面粗糙度Sa为0.08μm。当剥离EVOH层以测定OPP膜的表面粗糙度Sa时,该值为0.23μm。在上述条件下使用三维非接触表面形状测量***(Vertscan R3300h Lite、“株式会社菱化システム”制)测定表面粗糙度Sa。
使用电子束加热型的真空蒸镀装置,在EVOH层的表面上形成SiOx膜(金属氧化物层)。即,通过电子束加热使SiO蒸镀材料蒸发,从而形成了SiOx膜(厚度50nm)。接着,在SiOx膜的表面上形成含有PVA和TEOS的层(第2聚乙烯醇类树脂层)。即,将TEOS、甲醇和盐酸(0.1N)以质量比为18/10/72的方式混合,得到水解后的溶液(TEOS含有液)。通过将PVA的5%水溶液与TEOS含有液以PVA与TEOS的质量比为50/50的方式混合,制备了涂布液。将该涂布液涂布在SiOx膜的表面后使其干燥,从而形成了含有PVA和TEOS的层(PVA/TEOS=50/50)。
通过粘接剂(A-525、“三井化学株式会社製”)将聚丙烯类密封剂膜粘合在经由上述工序而得到的阻气层叠体的内表面上,从而制作了包装材料。包装材料的聚丙烯类树脂的质量比为94质量%。测定该包装材料的氧透过率。使用OX-TRAN2/20(MOCON公司制),根据JIS K 7126-2在温度30℃和相对湿度70%的条件下进行氧透过率的测定。此外,同样地测定了煮沸处理后的包装材料的氧透过率。即,使用包装材料制作三边小袋后,将自来水密封在其中。将该密封体在90℃的温度条件下煮沸处理30分钟后,测定包装材料的氧透过率。结果示于表1。
(实施例2)
除了形成AlOx膜(50nm)以代替SiOx膜(50nm)作为金属氧化物层以外,与实施例1同样地制作阻气层叠体和包装材料,并进行各评价。AlOx膜是通过电子束加热使铝锭蒸发并导入氧而形成的。结果示于表1。
(实施例3)
除了形成PVA与TEOS的质量比为97/3的层以代替形成PVA与TEOS的质量比为50/50的层以外,与实施例1同样地制作阻气层叠体和包装材料,并进行各评价。结果示于表1。
(比较例1)
除了不形成PVA与TEOS的质量比为50/50的层、而是在OPP膜的表面上直接形成SiOx膜(50nm)以外,与实施例1同样地制作阻气层叠体和包装材料,并进行各评价。结果示于表2。
(比较例2)
除了形成PVA层(每单位面积的质量为2.8g/m2、厚度为2.3μm)以代替形成EVOH层(每单位面积的质量为0.97g/m2、厚度为0.8μm)作为第1聚乙烯醇类树脂层以外,与实施例1同样地制作阻气层叠体和包装材料,并进行各评价。结果示于表2。
(比较例3)
除了形成EVOH层(每单位面积的质量为0.40g/m2、厚度为0.33μm)以代替EVOH层(每单位面积的质量为0.97g/m2、厚度为0.8μm)作为第1聚乙烯醇类树脂层以外,与实施例1同样地制作阻气层叠体和包装材料,并进行各评价。结果示于表2。
[表1]
[表2]
根据本公开,可以提供一种可用于实现包装材料的优异的可再利用性并且具有优异的阻气性的阻气层叠体。根据本公开,可以提供一种使用了该阻气层叠体的包装材料。
符号的说明
1…基材层、1a…涂层(密合层)、1b…共聚物层、3a…第1聚乙烯醇类树脂层、3b…第2聚乙烯醇类树脂层、5…金属氧化物层、10…阻气层叠体、10F…内表面、20…聚丙烯类密封剂层、50,60…包装材料、F1…聚丙烯类基材层的层叠面、F2…聚丙烯类基材层的外表面、F3…第1聚乙烯醇类树脂层的表面
Claims (13)
1.一种阻气层叠体,具有层叠结构,该层叠结构依次具备:
聚丙烯类基材层;
第1聚乙烯醇类树脂层;以及
金属氧化物层,
所述第1聚乙烯醇类树脂层的每单位面积的质量为0.5~2.5g/m2。
2.根据权利要求1所述的阻气层叠体,其中,
所述第1聚乙烯醇类树脂层的与所述金属氧化物层接触的一侧的表面粗糙度Sa为0.2μm以下。
3.根据权利要求1所述的阻气层叠体,其中,
所述第1聚乙烯醇类树脂层的与所述金属氧化物层接触的一侧的表面粗糙度Sa为0.1μm以下。
4.根据权利要求1至3中任一项所述的阻气层叠体,其中,
所述聚丙烯类基材层为丙烯的单聚物层。
5.根据权利要求1至4中任一项所述的阻气层叠体,进一步具备:
与所述第1聚乙烯醇类树脂层一起夹着所述金属氧化物层的第2聚乙烯醇类树脂层。
6.根据权利要求5所述的阻气层叠体,其中,
所述第2聚乙烯醇类树脂层含有硅烷化合物。
7.根据权利要求6所述的阻气层叠体,其中,
所述硅烷化合物相对于所述第2聚乙烯醇类树脂层的质量的质量比为0.05~0.95。
8.根据权利要求5至7中任一项所述的阻气层叠体,其中,
所述第2聚乙烯醇类树脂层的厚度为0.1~1.0μm。
9.根据权利要求1至8中任一项所述的阻气层叠体,其中,
所述第1聚乙烯醇类树脂层的厚度为0.4~2.0μm。
10.根据权利要求1至9中任一项所述的阻气层叠体,其中,
所述金属氧化物层是厚度为5~100nm的蒸镀层。
11.根据权利要求1至10中任一项所述的阻气层叠体,其中,
在所述聚丙烯类基材层的要设置所述第1聚乙烯醇类树脂层的一侧的相反侧的表面上进一步具有丙烯与其他单体的共聚物层,
所述其他单体为乙烯和丁烯中的至少一者。
12.根据权利要求1至11中任一项所述的阻气层叠体,其中,
在聚丙烯类基材层与第1聚乙烯醇类树脂层之间进一步具有密合层。
13.一种包装材料,具有:
权利要求1至12中任一项所述的阻气层叠体;以及
设置在所述阻气层叠体的表面上的聚丙烯类密封剂层,
以包装材料的总质量为基准,所述聚丙烯类基材层和所述聚丙烯类密封剂层的合计质量比率为85质量%以上。
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JP7259623B2 (ja) | 2023-04-18 |
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WO2021020401A1 (ja) | 2021-02-04 |
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