CN108472940A - 多层体、包装容器和食品的保存方法 - Google Patents

多层体、包装容器和食品的保存方法 Download PDF

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Publication number
CN108472940A
CN108472940A CN201780006018.4A CN201780006018A CN108472940A CN 108472940 A CN108472940 A CN 108472940A CN 201780006018 A CN201780006018 A CN 201780006018A CN 108472940 A CN108472940 A CN 108472940A
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China
Prior art keywords
layer
layered body
oxygen
food
mass
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Granted
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CN201780006018.4A
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CN108472940B (zh
Inventor
井上敦
伊东芳树
田中友辅
新见健
新见健一
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Abstract

一种多层体,其具备:含有热塑性树脂的密封层(A);含有热塑性树脂和铁粉的吸氧层(B);以及,具有氧阻隔性的氧阻隔层(D),且各层以前述的顺序依次层叠,密封层(A)和氧阻隔层(D)中的至少一者含有离聚物作为热塑性树脂。

Description

多层体、包装容器和食品的保存方法
技术领域
本发明涉及多层体、包装容器和食品的保存方法。
背景技术
以往,为了防止以食品、饮料、药品、医疗品、化妆品、金属制品和电子制品为代表的容易受氧影响而变质或劣化的各种物品的氧化而长期保存,可以使用收纳它们的包装容器、包装袋内进行氧去除的脱氧剂。
作为该脱氧剂,初期被开发并目前也较多使用的形态为将包含粉状或粒状的铁粉、抗坏血酸等的脱氧剂装填于透气性的小袋。
近年来,还利用了操作更容易且应用范围宽、误食的可能性极其小的薄膜状的脱氧剂。作为这样的薄膜状的脱氧剂,提出了各种形态。
例如,专利文献1中,想要提供抑制臭气原因物质的层叠薄膜,其为依次层叠外层/第1粘接层/阻隔层/第2粘接层/吸氧层/化学吸附层/密封层而形成的层叠薄膜,吸氧层中使用铁粉系吸氧剂。产生的臭气原因物质为醛类、酸类,提出了,化学吸附层中使用将臭气原因物质以化学的方式吸附的负载胺系化合物的二氧化硅的层叠薄膜。
另外,专利文献2中,想要提供吸氧性能优异的吸氧剂(吸氧材料)等,提出了一种吸氧剂,其特征在于,含有主链上具有乙烯单元和羰基的聚合物或乙烯·不饱和羧酸共聚物的离聚物。专利文献2中报道了,上述聚合物和离聚物具有吸氧能力,能通过进行光或能量射线照射或加热而引发氧化反应。
现有技术文献
专利文献
专利文献1:日本特开2012-240329号公报
专利文献2:日本特开2005-87991号公报
发明内容
发明要解决的问题
然而,如果将专利文献1中记载的层叠薄膜用于食品的保存用途,则从食品释放的水分在与吸氧层接触前会与吸臭气层接触,因此水分被吸臭气层吸收,而供给至吸氧层的水分量相应地减少。其结果,吸氧量减少,吸氧速度也会变慢。
另外,专利文献2中,其实施例中公开了包含离聚物和作为金属催化剂的钴的吸氧剂,该技术是以钴为催化剂,离聚物与氧发生反应,从而离聚物吸收氧。然而,由于离聚物本身的吸氧能力不高,因此作为其结果,吸氧速度也会变慢。
进而专利文献2完全没有提及关于吸臭气。
结果,任意文献中记载的层叠薄膜、吸氧剂均在保持优异的吸氧性的同时使臭气减少的方面有进一步改善的余地。
进而,使用脱氧剂时,食品被密闭于阻气性的容器。因此,臭气被封入容器内,源自臭气的恶臭、食品味道的恶化成为问题。作为臭气的产生原因,考虑有来自食品的臭气的产生、脱氧剂在吸收氧时伴随的脱氧剂物质的分解所导致的臭气的产生、食品中的物质与脱氧剂接触而导致的臭气的产生等。
本发明是鉴于上述情况而作出的,其目的之一在于,提供:保持优异的吸氧性的同时能够充分抑制臭气的多层体、使用该多层体的包装容器、和使用该包装容器的食品的保存方法。
另外,本发明的另一目的在于,提供:封入食品并保管时、减少臭气、且抑制来自外界气体的氧的透过从而能较高地维持食品的风味的多层体、使用该多层体的包装容器、和使用该包装容器的食品的保存方法。
用于解决问题的方案
本发明人等为了达成上述目的反复深入研究,结果发现:通过使用包含特定成分的吸氧层和/或密封层,从而可以提供:保持优异的吸氧性的同时能够充分抑制臭气的多层体、使用该多层体的包装容器、和使用该包装容器的食品的保存方法,至此完成了本发明。进而发现:通过将这样的多层体等用于食品的保管,从而减少臭气,并且抑制来自外界气体的氧的透过,由此能较高地维持食品的风味,至此完成了本发明。
即,本发明如下述。
(1)一种多层体,其具备:含有热塑性树脂的密封层(A);含有热塑性树脂和铁粉的吸氧层(B);以及,具有氧阻隔性的氧阻隔层(D),且各层以前述的顺序进行层叠,
前述密封层(A)和前述吸氧层(B)中的至少一者含有离聚物作为前述热塑性树脂。
(2)根据(1)所述的多层体,其中,在前述吸氧层(B)与前述氧阻隔层(D)之间还具备含有热塑性树脂和无机碱的吸臭气层(C)。
(3)根据(2)所述的多层体,其中,前述无机碱为具有钙的无机碱。
(4)一种包装容器,其以使含有热塑性树脂的密封层(A)为内侧、且使具有氧阻隔性的氧阻隔层(D)为外侧的方式具备(1)~(3)中任一项所述的多层体。
(5)一种食品的保存方法,其通过(4)所述的包装容器封入食品并保存。
(6)根据(5)所述的保存方法,其中,前述食品具有0.3以上且1.0以下的水分活度(Aw)。
(7)根据(5)或(6)所述的保存方法,其中,前述食品为包含1质量%以上且50质量%以下的脂质的、巧克力点心和肉类中的任一者。
发明的效果
根据本发明,可以提供具备优异的吸氧性的同时能够充分抑制臭气的多层体、使用该多层体的包装容器、和使用该包装容器的食品的保存方法。另外,根据本发明,可以提供封入食品并保管时、减少臭气、且抑制来自外界气体的氧的透过从而能较高地维持食品的风味的多层体、使用该多层体的包装容器、和使用该包装容器的食品的保存方法。
附图说明
图1为示意性示出本发明的多层体的一例的部分剖视图。
图2为示意性示出本发明的包装容器的一例的部分剖视图。
具体实施方式
以下,根据需要参照附图、并对用于实施本发明的方式(以下,简单称为“本实施方式”)进行详细说明,但本发明不限定于下述本实施方式。本发明在不脱离其主旨的范围内可以进行各种变形。需要说明的是,附图中,对同一要素标注同一符号,省略重复的说明。另外,上下左右等位置关系只要没有特别限定,就基于附图所示的位置关系。进而,附图的尺寸比率不限定于图示的比率。另外,本说明书中的“(甲基)丙烯酸”是指“丙烯酸”和与其对应的“甲基丙烯酸”。
(多层体)
图1为示意性示出本实施方式的多层体的一例的部分剖视图。该多层体具备:含有热塑性树脂的密封层(A);含有热塑性树脂和铁粉的吸氧层(B);以及,具有氧阻隔性的氧阻隔层(D),且各层以该顺序进行层叠,密封层(A)和吸氧层(B)中的至少一者含有离聚物作为热塑性树脂。
另外,吸氧层(B)中所含的吸氧性的物质为铁粉,因此,与吸氧性的物质为有机高分子化合物的情况不同,即使吸收氧也不分解,可以抑制产生臭气、或吸氧层(B)的物理强度降低。进而,本实施方式中,通过密封层(A)和/或吸氧层(B)含有离聚物,从而可以充分抑制臭气的产生。作为该臭气产生抑制原理,本发明人等认为是由于,与离聚物吸收臭气的情况相比,还抑制例如食品中的物质、特别是油脂、脂肪酸类与吸氧层(B)中的铁粉接触而产生臭气。即,本发明人等推定离聚物妨碍油脂、脂肪酸类与铁粉的物理接触,从而臭气的产生被抑制。但是,因素不限定于此。另外,本实施方式的多层体由于在比吸氧层(B)更靠近外侧具备密封层(A),因此吸氧层(B)不与食品直接接触而溶出于水,可以防止该层中所含的铁粉引起的食品的风味降低。
多层体可以根据其用途而适宜设定厚度,例如可以为厚度为30μm以上且250μm以下的多层薄膜,也可以为厚度超过250μm且3000μm以下的多层片。更具体而言,例如用于保存后述的巧克力点心的软包装容器使用本实施方式的多层体的情况下,从需要保持薄且柔软性的观点出发,多层体优选厚度为30μm以上且250μm以下的多层薄膜。另外,用于保存后述的肉类的泡(blister)、盘形状的硬质包装容器使用本实施方式的多层体的情况下,从为了保持泡、盘等特定的形状所需要的硬度的观点出发,多层体优选厚度超过250μm且3000μm以下的多层片。
(密封层(A))
本实施方式的密封层(A)至少含有热塑性树脂。密封层(A)发挥作为密封剂的作用,并且在使用本实施方式的多层体的包装容器中,还能发挥将食品那样的收纳物与吸氧层(B)隔离而不使其接触的作用。另外,密封层(A)还能发挥进行有效的氧透过的作用,以使基于吸氧层(B)的迅速吸氧不受到妨碍。
密封层(A)的透氧率优选1000cc/(m2·24h·atm)以上。由此,能进一步提高本实施方式的多层体吸收氧的速度。透氧率是使用“OX-TRAN-2/21(MOCON公司制)”、在测定温度25℃、单元面积50cm2的条件下测定的。
作为密封层(A)中所含的热塑性树脂,例如可以举出聚乙烯、乙烯-α-烯烃共聚物、聚丙烯、丙烯-乙烯无规共聚物、丙烯-乙烯嵌段共聚物、乙烯-环状烯烃共聚物等聚烯烃树脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸甲酯、乙烯-乙酸乙烯酯共聚物等乙烯系共聚物、聚丁二烯、聚异戊二烯、苯乙烯-丁二烯共聚物等合成橡胶系树脂和其氢化树脂、软质聚氯乙烯、聚苯乙烯、聚甲基戊烯、有机硅树脂、聚硅氧烷与其他树脂的共聚物、和离聚物。热塑性树脂可以单独使用1种或组合2种以上使用。其中,从进一步提高抑制臭气的产生的效果的观点出发,热塑性树脂优选包含离聚物。
密封层(A)中的热塑性树脂的含量相对于密封层(A)的整体量(100质量%),优选70质量%以上且100质量%以下、更优选80质量%以上且100质量%以下、进一步优选90质量%以上且100质量%以下。通过热塑性树脂的含量处于上述范围内,可以更有效且确实地发挥密封层(A)的上述作用。
密封层(A)的厚度优选5μm以上且500μm以下、更优选10μm以上且250μm以下。通过密封层(A)的厚度处于上述范围内,进一步加快多层体吸收氧的速度,并且更有效且确实地发挥将上述收纳物与吸氧层(B)隔离而不使其接触的作用。
密封层(A)只要不妨碍发挥上述作用就可以含有除热塑性树脂以外的材料。作为这样的材料,例如可以举出碳酸钙、粘土、云母、二氧化硅等填充剂、干燥剂、颜料、染料、抗氧化剂、增滑剂、防静电剂、稳定剂、和增塑剂,但不特别限定于这些。它们可以单独使用1种或组合2种以上使用。
(吸氧层(B))
本实施方式的吸氧层(B)含有热塑性树脂和铁粉。吸氧层(B)发挥吸收想要透过多层体的氧的作用,例如吸收想要从外界气体浸入至使用本实施方式的多层体的包装容器的内部的氧、以及吸收残留于该包装容器内部的氧。
作为热塑性树脂,可以适宜使用公知的热塑性树脂,没有特别限定,例如可以举出低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、线状低密度聚乙烯、线状超低密度聚乙烯、聚丙烯、聚-1-丁烯、和聚-4-甲基-1-戊烯、或、乙烯、丙烯、1-丁烯、和4-甲基-1-戊烯等α-烯烃彼此的无规或嵌段共聚物等聚烯烃、以及离聚物、或它们的混合物。热塑性树脂可以单独使用1种或组合2种以上使用。其中,从进一步提高抑制臭气产生的效果的观点出发,热塑性树脂优选包含离聚物。
吸氧层(B)中的热塑性树脂的含量没有特别限定,相对于吸氧层(B)的整体量(100质量%),可以为45质量%以上且85质量%以下,也可以为50质量%以上且80质量%以下,还可以为55质量%以上且75质量%以下。
作为铁粉,只要是铁的表面露出了就没有特别限定,可以适合使用本领域中公知的铁粉、例如还原铁粉、电解铁粉和喷雾铁粉。此外,也可以使用铸铁等粉碎物、切削品等。它们可以单独使用1种或组合2种以上使用。铁粉与浸入至吸氧层(B)的水发生反应,从而具有吸氧能力。
铁粉的平均粒径优选0.1μm以上且200μm以下、更优选1μm以上且50μm以下。通过使铁粉的平均粒径处于上述范围内,与氧的接触变得更良好,吸氧层(B)中的吸氧能力提高,并且可以进一步提高吸氧层(B)的薄膜形成能力。铁粉的平均粒径通过日机装株式会社制的MICROTRACK MT3000II(商品名)、株式会社岛津制作所制的激光衍射式粒度分布测定器SALD-3000(商品名)等粒径测定装置而测定。
铁粉的含量没有特别限定,相对于吸氧层(B)的整体量(100质量%),优选10.0质量%以上且60质量%以下、更优选15质量%以上且50质量%以下、进一步优选20质量%以上且40质量%以下。由此,进一步提高吸氧层(B)的吸氧能力,并且进一步抑制铁粉所导致的源自食品的油等的分解,因此可以进一步减少成为恶臭的原因的气体的产生。
吸氧层(B)只要不妨碍发挥上述作用就可以包含除热塑性树脂和铁粉以外的材料。作为这样的材料,例如可以举出干燥剂、吸附剂、抗菌剂、着色剂和除臭剂。它们可以单独使用1种或组合2种以上使用。
干燥剂是指,从空气中吸收水分的剂,例如可以举出硅胶、生石灰(氧化钙)、氯化钙、五氧化二磷和氧化铝。另外,吸附剂是指,使原子、分子、微粒等以物理的方式固定于其表面的剂,具体而言,可以举出活性炭、沸石、硅胶和氧化铝。其中,硅胶、氧化铝还具有作为干燥剂的功能,故优选。需要说明的是,吸氧层(B)含有干燥剂、吸附剂时,其含量优选少于铁粉(例如,相对于吸氧层(B)的整体量,超过0.0%且低于5.0%)。干燥剂、吸附剂通常具有吸水性,因此,通过使它们的含量少于铁粉,可以提高铁粉与水的反应性。
吸氧层(B)的厚度没有特别限定,优选10μm以上且100μm以下、更优选20μm以上且75μm以下。由此,可以进一步加快多层体吸收氧的速度,并且可以防止多层体的柔软性受损。
(离聚物)
对于本实施方式的多层体,上述密封层(A)和吸氧层(B)中的至少一者含有离聚物作为热塑性树脂。作为离聚物,没有特别限定,从更有效且确实地发挥本发明的作用效果的观点出发,优选乙烯与不饱和羧酸的共聚物的离聚物、和乙烯与不饱和羧酸与不饱和羧酸酯的共聚物的离聚物。
作为上述不饱和羧酸,从与上述同样的观点出发,优选α,β-不饱和羧酸,具体而言,可以举出丙烯酸、甲基丙烯酸和马来酸,更优选甲基丙烯酸。另外,作为上述不饱和羧酸酯,从与上述同样的观点出发,优选α,β-不饱和羧酸酯,具体而言,可以举出丙烯酸酯、甲基丙烯酸酯和马来酸酯,更优选甲基丙烯酸酯。作为构成酯的醇成分,从与上述同样的观点出发,优选碳原子数1~10的直链或支链的醇,具体而言,可以举出甲醇、乙醇、异丙醇、正丙醇、异丁醇、正丁醇、仲丁醇、正己醇、正辛醇、2-乙基己醇和正癸醇。
作为不饱和羧酸酯,更具体而言,可以举出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苯酯和马来酸二甲酯。
乙烯与不饱和羧酸的共聚物中,以共聚物为基准(100质量%),源自乙烯的结构单元的含有比率优选20质量%以上且99质量%以下、更优选30质量%以上且97质量%以下,源自(甲基)丙烯酸的结构单元的含有比率优选1质量%以上且80质量%以下、更优选3质量%以上且70质量%以下。
乙烯与不饱和羧酸与不饱和羧酸酯的共聚物中,以共聚物为基准(100质量%),源自乙烯的结构单元的含有比率优选20质量%以上且98质量%以下、更优选25质量%以上且94质量%以下,源自不饱和羧酸的结构单元的含有比率优选1质量%以上且80质量%以下、更优选3质量%以上且70质量%以下,源自(甲基)丙烯酸酯的结构单元的含有比率优选1质量%以上且80质量%以下、更优选3质量%以上且75质量%以下。
乙烯与(甲基)丙烯酸的共聚物的离聚物、和乙烯与不饱和羧酸与不饱和羧酸酯的共聚物的离聚物是其羧基的一部分或全部被金属离子中和而得到的。其中和度例如可以为0.1摩尔%以上,优选1摩尔%以上、更优选10摩尔%以上。
作为金属离子的金属种类,例如可以举出锂、钠、钾、钙、镁、锌、钴、镍、锰、铅、铜、钛、铁、铝和锆。其中,从更有效且确实地发挥本发明的作用效果的观点出发,优选选自由周期表第1族和第12族组成的组中的金属种类,更优选钠、钾和锌,进一步优选钠和锌,特别优选钠。另外,除金属离子之外,也可以包含以氨、甲基胺、二甲基胺、三甲基胺、乙基胺、二乙基胺、三乙基胺、亚乙基二胺、二亚乙基三胺、三亚乙基四胺和1,3-二甲基氨基环己烷等为代表的氨基化合物。它们可以使用1种或2种以上。
上述离聚物的190℃、2160g载荷下的熔体流动速率(MFR)优选0.01g/10分钟以上且1000g/10分钟以下、更优选0.1g/10分钟以上且100g/10分钟以下。
密封层(A)和/或吸氧层(B)中所含的热塑性树脂中的离聚物的含量中,密封层(A)中的离聚物的含量相对于密封层(A)的整体量(100质量%),优选10质量%以上且100质量%以下、更优选20质量%以上且90质量%以下。另外,吸氧层(B)中的离聚物的含量相对于吸氧层(B)的整体量(100质量%),优选10质量%以上且90质量%以下、更优选20质量%以上且90质量%以下。通过使各层中的离聚物的含量为上述下限值以上,妨碍源自食品的油脂、脂肪酸类与铁粉的物理接触,有被推定抑制臭气产生的离聚物的臭气产生抑制效果进一步提高的倾向。另外,吸氧层(B)的厚度相对于密封层(A)的厚度之比((B)/(A))优选0.02以上且20以下、更优选0.08以上且7.5以下。
(氧阻隔层(D))
氧阻隔层(D)是具有氧阻隔性的层,例如通过包含氧阻隔性物质,从而可以具备其氧阻隔性。氧阻隔性物质是指,透氧率为100cc/(m2·24h·atm)以下的物质。作为氧阻隔层(D)中能包含的氧阻隔性物质,例如可以举出蒸镀有二氧化硅或氧化铝的聚酯(例如聚对苯二甲酸乙二醇酯)、聚酰胺、尼龙MXD6、乙烯-乙烯基醇共聚物和偏二氯乙烯。另外,氧阻隔层(D)可以为铝箔等金属箔。氧阻隔层(D)的厚度优选1μm以上且300μm以下、更优选1μm以上且100μm以下。通过氧阻隔层(D)的厚度处于上述范围内,从而可以进一步提高阻氧效果,并且可以防止柔软性受损。作为透氧率的测定方法,可以使用作为密封层(A)的透氧率的测定方法的示例的方法。
(吸臭气层(C))
本实施方式的多层体优选在吸氧层(B)与氧阻隔层(D)之间还具备含有热塑性树脂和无机碱的吸臭气层(C)。吸臭气层(C)发挥吸收与多层体接触的臭气的作用。在使用本实施方式的多层体的包装容器中,可以吸收从食品那样的收纳物产生的臭气。另外,如果使用这样的多层体,则即使具备吸臭气层(C),从食品释放的水分与吸臭气层(C)接触之前也与吸氧层(B)接触,因此,供给至吸氧层(B)的水分量不会减少,其结果,可以防止吸氧量减少、或吸氧速度变慢。进而,上述方式中,具备吸臭气层(C)的多层体由于在比含有无机碱的吸臭气层(C)更靠近外侧具备密封层(A),因此,含有无机碱的吸臭气层(C)不会与食品直接接触并溶出于水,可以防止该层中所含的无机碱引起的食品的风味降低。
作为热塑性树脂,可以适宜使用公知的热塑性树脂,没有特别限定,例如可以举出低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、线状低密度聚乙烯、线状超低密度聚乙烯、聚丙烯、聚-1-丁烯、聚-4-甲基-1-戊烯、或乙烯、丙烯、1-丁烯、4-甲基-1-戊烯等α-烯烃彼此的无规或嵌段共聚物等聚烯烃、或它们的混合物。热塑性树脂可以单独使用1种或组合2种以上使用。
吸臭气层(C)中的热塑性树脂的含量没有特别限定,相对于吸臭气层(C)的整体量(100质量%),可以为70质量%以上且98质量%以下,也可以为75质量%以上且98质量%以下,还可以为80质量%以上且95质量%以下。
无机碱是显示碱性的无机化合物,用于吸收成为臭气的原因的气体。作为无机碱,例如可以举出周期表第1族和第2族的金属的氢氧化物、碳酸盐、碳酸氢盐和氧化物。更具体而言,可以举出氢氧化锂、氢氧化钠、氢氧化钾、氢氧化铷、氢氧化铯、氢氧化钙、氢氧化锶、氢氧化钡、氢氧化镁、碳酸钠、碳酸钾、碳酸钙、碳酸镁、碳酸氢钠、碳酸氢钾、碳酸氢钙、氧化钙和氧化镁。其中,从更有效且确实地发挥本发明的作用效果的观点出发,优选具有周期表第2族的金属的无机碱,更优选具有钙或镁的无机碱,进一步优选具有钙的无机碱,更进一步优选氧化钙、氢氧化钙、选自由氧化钙和氢氧化钙组成的组中的1种以上的无机碱,特别优选选自由氧化钙和氢氧化钙组成的组中的1种以上的无机碱。
无机碱的平均粒径优选0.1μm以上且200μm以下、更优选1μm以上且50μm以下。通过使无机碱的平均粒径处于上述范围内,与臭气的接触变得更良好,吸臭气层(C)中的吸臭气能力提高,并且可以进一步提高吸臭气层(C)的薄膜形成能力。无机碱的平均粒径通过日机装株式会社制的MICROTRACK MT3000II(商品名)、株式会社岛津制作所制的激光衍射式粒度分布测定器SALD-3000(商品名)等粒径测定装置而测定。
吸臭气层(C)中的无机碱的含量相对于吸臭气层(C)的整体量(100质量%),优选0.10质量%以上且20.0质量%以下、更优选0.50质量%以上且17.0质量%以下、进一步优选1.0质量%以上且15.0质量%以下。无机碱的含量处于上述范围内时,吸臭气层(C)中的吸臭气能力进一步提高,并且可以进一步抑制随着吸臭气层(C)吸收水分的吸氧层(B)的吸氧能力的降低。
吸臭气层(C)只要不妨碍发挥上述作用就可以含有除热塑性树脂和无机碱以外的材料。作为这样的材料,例如可以举出干燥剂、吸附剂、抗菌剂、着色剂和除臭剂(其中,不包括相当于无机碱的物质)。它们可以单独使用1种或组合2种以上使用。干燥剂和吸附剂可以举出与上述同样的物质。需要说明的是,吸臭气层(C)包含干燥剂、吸附剂时,其含量优选少于无机碱。由此,无机碱在吸臭气层(C)内不均匀存在,从而可以进一步抑制该吸臭气层(C)内不存在的部位产生。
吸臭气层(C)的厚度没有特别限定,优选1μm以上且300μm以下、更优选10μm以上且200μm以下。由此,可以进一步提高多层体的吸臭气能力,并且可以防止多层体的柔软性受损。
(其他层)
本实施方式的多层体在上述密封层(A)、吸氧层(B)、氧阻隔层(D)和任意具备的吸臭气层(C)的基础上,在不妨碍本发明的目的达成的范围内也可以具备除这些以外的层。作为这样的层,例如可以举出粘接层、遮光层、易剥离层和易撕裂层。
对于本实施方式的多层体,例如从进一步提高相邻的2个层之间的粘接强度的观点出发,该2个层之间可以具备粘接层。粘接层优选包含具有粘接性的热塑性树脂。作为具有粘接性的热塑性树脂,例如可以举出:将聚乙烯或聚丙烯等聚烯烃系树脂用丙烯酸、甲基丙烯酸、马来酸、马来酸酐、富马酸、衣康酸等不饱和羧酸改性而成的酸改性聚烯烃树脂;以聚酯系嵌段共聚物为主成分的聚酯系热塑性弹性体。需要说明的是,粘接层的厚度没有特别限定,从发挥实用的粘接强度且确保成形加工性的观点出发,优选2μm以上且100μm以下。
另外,对于本实施方式的多层体,从进一步提高遮光性的观点出发,特别是使用不具有金属的层作为上述氧阻隔层(D)的情况下,在氧阻隔层(D)的与吸氧层(B)为相反侧可以具备遮光层。作为遮光层,例如可以举出金属箔和蒸镀膜。此处,作为金属箔,没有特别限定,优选铝箔。另外,从遮光性和耐弯曲性等观点出发,金属箔的厚度优选3μm以上且50μm以下、更优选3μm以上且30μm以下,进一步优选5μm以上且15μm以下。作为蒸镀膜,没有特别限定,例如可以举出蒸镀有铝、氧化铝等金属或金属氧化物那样的金属化合物的膜的树脂薄膜。需要说明的是,作为蒸镀膜的形成方法,例如可以举出如下方法:利用真空蒸镀法、溅射法、离子镀法等物理蒸镀法、PECVD等化学蒸镀法等,将金属或金属化合物蒸镀在树脂薄膜上。从遮光性和耐弯曲性等观点出发,蒸镀膜的厚度优选5nm以上且500nm以下、更优选5nm以上且200nm以下。
进而,将本实施方式的多层体作为后述的包装容器等使用的情况下,为了使该包装容器的开封容易,多层体可以包含易剥离层或易撕裂层。作为易剥离层,例如一般已知有将2种以上的不同的聚烯烃共混、并控制了密封强度和剥离强度的薄膜。另外,作为易撕裂层,例如一般已知有尼龙6中共混有尼龙MXD6的易撕裂性薄膜。
(多层体的制造方法)
本实施方式的多层体例如可以将依次层叠有包含密封层(A)的材料的树脂组合物、包含吸氧层(B)的材料的树脂组合物和包含氧阻隔层(D)的材料的组合物的包含多层结构的层叠体利用多层膜制造装置进行共挤出,从而制造。或,可以将依次层叠有包含密封层(A)的材料的树脂组合物和包含吸氧层(B)的材料的树脂组合物的包含多层结构的层叠体利用多层膜制造装置进行共挤出而制造,然后,使用粘接剂,将氧阻隔层(D)粘接于吸氧层(B)。多层体在吸氧层(B)与氧阻隔层(D)之间具备吸臭气层(C)的情况下,例如可以如下制造:将依次层叠有包含密封层(A)的材料的树脂组合物、包含吸氧层(B)的材料的树脂组合物、包含吸臭气层(C)的材料的树脂组合物和包含氧阻隔层(D)的材料的组合物的包含多层结构的层叠体利用多层膜制造装置进行共挤出,从而制造。或,可以将依次层叠有包含密封层(A)的材料的树脂组合物、包含吸氧层(B)的材料的树脂组合物和包含吸臭气层(C)的材料的树脂组合物的包含多层结构的层叠体利用多层膜制造装置进行共挤出而制造,然后使用粘接剂将氧阻隔层(D)粘接于吸臭气层(C)。另外,共挤出中,在各层间可以根据需要设置粘接层。
(包装容器)
本实施方式的多层体可以用于作为脱氧性的包装材料的包装袋等包装容器的一部分或全部。图2为示出本实施方式的脱氧性的包装容器的一例的部分剖视图,示出使用图1所示的多层体的吸氧层(B)与氧阻隔层(D)之间还具备吸臭气层(C)的多层体的例子。图2所示的包装容器100具备2个多层体10。2个多层体10在彼此以密封层(A)为内侧的状态下被粘贴。包装容器100例如通过将多层体10的缘部彼此热封而制造。该包装容器100使密封层(A)为内侧(即与收纳物接触的一侧)、且使氧阻隔层(D)为外侧(即与外界气体直接接触的一侧)。需要说明的是,本实施方式的包装容器只要以使密封层(A)为内侧、且使氧阻隔层(D)为外侧的方式具备本实施方式的多层体,就不限定于图2所示的包装容器100。图2所示的包装容器100示出将多层体用于包装容器的全部的例子,但也可以将多层体用于例如仅容器的盖材、袋包的单面那样的包装容器的一部分。
进而,本实施方式的多层体可以作为加工成片状或薄膜状的脱氧剂、或将其放入至透气性小袋的形态的脱氧剂包装体使用。另外,本实施方式的多层体可以成型为标签、卡和打包(packing)等形态作为脱氧体使用。
对本实施方式的多层体的用途没有限制,在食品、饮料、药品、医疗品、化妆品、金属制品和电子制品等保存和品质保持的领域中,发挥实用性高的脱氧性能和吸臭气能力。其中,在食品的保存领域中,可以发挥特别有效高的脱氧性能和吸臭气能力。
(食品的保存方法)
本实施方式的食品的保存方法是通过上述本实施方式的包装容器封入食品并保存的方法。本实施方式中,氧的吸收(脱氧)取决于吸氧层(B)中与水分发生反应的铁粉,因此,食品优选包含规定量的水分。具体而言,食品的水分活度(Aw)优选0.3以上且1.0以下。此处,水分活度是指,表示物品中的自由水含量的尺度,用0.0以上且1.0以下的数字表示,无水分的物品成为0.0,纯水成为1.0。即,将该物品密封并达到平衡状态后的空间内的水蒸气压设为P、纯水的水蒸气压设为P0、同空间内的相对湿度设为RH(%)的情况下,某一物品的水分活度(Aw)用下述式定义。
Aw=P/P0=RH/100
本实施方式的食品的保存方法中,作为成为保存对象的食品,例如可以举出巧克力点心、果肉果冻、羊羹、布丁等点心类、菠萝、橘子、桃、杏子、梨、苹果等水果类、生菜、萝卜、黄瓜等蔬菜类、牛肉、猪肉、鸡肉等肉类、液体汤汁、蛋黄酱、味噌、磨碎香辛料等调料、以果酱、奶油、巧克力糊等糊状食品、以咖喱、液体汤、炖菜、酱菜、炖汤等液体加工食品为代表的液体系食品、以饮料水、茶饮料、咖啡饮料、清凉饮料水、酒精饮料、牛奶为代表的饮料、荞麦面、乌冬面、拉面等生面条和煮面条、精米、调湿米、免洗米等烹饪前的米类、经过烹饪的熟米、米饭、红米饭、米粥等加工米制品类、以粉末汤、汤料等粉末调料等为代表的含水分食品。
其中,优选包含1质量%以上且50质量%以下的脂质的食品。这样的食品不仅容易因氧变质而且容易产生臭气。并且通过使用本实施方式的多层体作为包装容器等,更有效且确实地吸收产生的臭气。作为这样的食品,更具体而言,可以举出包含1质量%以上且50质量%以下的脂质的巧克力点心、和包含1质量%以上且50质量%以下的脂质的肉类(例如牛肉)。上述巧克力点心的情况下,在常温下保存时,本实施方式的包装容器等是特别有用的,肉类的情况下,在冷藏条件(例如5℃以上且10℃以下)下保存时,本实施方式的包装容器等是特别有用的。
实施例
以下,根据实施例对本发明进一步进行详细说明,但本发明不限定于这些实施例。
(多层体的评价方法1)
由多层体制作图2所示的袋状的包装容器。接着,在该包装容器中,与空气一起收纳包含巧克力、海绵蛋糕和鲜奶油的巧克力点心,然后密封。将放入了巧克力点心的包装容器在25℃下在暗处保存7天。之后,将包装容器开封,取出巧克力点心,将该巧克力点心的巧克力部分含于口中,确认此时的风味。将含于口中时香味和味道均良好的情况、即、基本没有确认到与保存前的变化的情况评价为“-”,将巧克力的味道得以保持、但巧克力的香味变弱、想起杏仁的恶臭明显的情况评价为“+”,将虽然感到巧克力的风味(香味和味道)、但其均变弱的情况评价为“++”,将感到与巧克力不同品质的味道的情况评价为“+++”。
(多层体的评价方法2)
由多层体制作图2所示的袋状的包装容器。接着,在该包装容器中与空气一起收纳包含巧克力、海绵蛋糕和鲜奶油的巧克力点心,然后密封。将放入了巧克力点心的包装容器在25℃下在暗处保存7天。从保存后的包装容器的开封口用注射器采集包装容器内的气体,使用氧浓度分析计(Dansensor公司制商品名“CheckMate2”),测定氧浓度(%)。
(实施例1)
将聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC8001”)67.5质量份、铁粉(IPROS CORPORATION制商品名“海绵状铁粉”、平均粒径30μm)30.0质量份和氧化钙(CalFine Inc.,制、平均粒径5μm)2.5质量份用具有2根直径37mm的螺杆的双螺杆混炼挤出机、以200℃进行熔融混炼,从挤出机头挤出线料,冷却后造粒,从而得到吸氧层(B1)用的树脂组合物(b1)。
另外,将聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC606”)94.2质量份和氧化钙(CalFine Inc.,制、平均粒径5μm)5.9质量份用上述双螺杆混炼挤出机、以200℃进行熔融混炼,从挤出机头挤出线料,冷却后造粒,从而得到吸臭气层(C1)用的树脂组合物(c1)。
接着,使用具备第1~第3挤出机、供料头、T模头、冷却辊和片牵引机的3层多层片成形装置,分别从第1挤出机挤出密封层(A1)用的离聚物(乙烯与甲基丙烯酸的共聚物的离聚物、金属离子的金属种类:钠、Du Pont-Mitsui Polychemicals Co.,Ltd.制商品名“HIMILAN 1601”)、从第2挤出机挤出上述树脂组合物(b1)、从第3挤出机挤出聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC606”),借助供料头得到3层薄膜。该3层薄膜的层构成从内层起为密封层(A1)(厚度20μm)/吸氧层(B1)(厚度45μm)/聚乙烯层(PE)(厚度23μm)。在所得3层薄膜的聚乙烯层(PE)侧上,以二氧化硅蒸镀面为粘接面、通过干层压粘接包含二氧化硅蒸镀聚对苯二甲酸乙二醇酯(TORAY ADVANCED FILM Co.,Ltd.制商品名“Barrialox”)的厚度12μm的氧阻隔层(D),得到多层体。
对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
(实施例2)
将离聚物(乙烯与甲基丙烯酸的共聚物的离聚物、金属离子的金属种类:钠、DuPont-Mitsui Polychemicals Co.,Ltd.制商品名“HIMILAN 1601”)67.5质量份、铁粉(IPROS CORPORATION制商品名“海绵状铁粉”、平均粒径30μm)30.0质量份和氧化钙(CalFine Inc.,制、平均粒径5μm)2.5质量份用具有2根直径37mm的螺杆的双螺杆混炼挤出机、以200℃进行熔融混炼,从挤出机头挤出线料,冷却后造粒,从而得到吸氧层(B2)用的树脂组合物(b2)。使用密封层(A2)用的聚乙烯(住友化学株式会社制商品名“SUMIKATHENEL705”)代替密封层(A1)用的离聚物(乙烯与甲基丙烯酸的共聚物的离聚物、金属离子的金属种类:钠、Du Pont-Mitsui Polychemicals Co.,Ltd.制商品名“HIMILAN 1601”),使用树脂组合物(b2)代替树脂组合物(b1),除此之外,与实施例1同样地,得到具备密封层(A2)代替密封层(A1)、具备吸氧层(B2)代替吸氧层(B1)的多层体。对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
(实施例3)
将聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC606”)88.3质量份和氧化钙(CalFine Inc.,制、平均粒径5μm)11.7质量份用上述双螺杆混炼挤出机、以200℃进行熔融混炼,从挤出机头挤出线料,冷却后造粒,从而得到吸臭气层(C3)用的树脂组合物(c3)。使用树脂组合物(c3)代替聚乙烯层(PE)用的聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC606”),除此之外,与实施例1同样地,得到具备吸臭气层(C3)代替聚乙烯层(PE)的多层体。对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
(实施例4)
使用树脂组合物(c3)代替聚乙烯层(PE)用的聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC606”),除此之外,与实施例2同样地,得到具备吸臭气层(C3)代替聚乙烯层(PE)的多层体。对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
(比较例1)
使用密封层(A2)用的聚乙烯(住友化学株式会社制商品名“SUMIKATHENE L705”)代替密封层(A1)用的离聚物(乙烯与甲基丙烯酸的共聚物的离聚物、金属离子的金属种类:钠、Du Pont-Mitsui Polychemicals Co.,Ltd.制商品名“HIMILAN 1601”),除此之外,与实施例1同样地,得到具备密封层(A2)代替密封层(A1)的多层体。对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
(比较例2)
将聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC8001”)64.6质量份、铁粉(IPROS CORPORATION制商品名“海绵状铁粉”、平均粒径30μm)30.0质量份和氧化钙(CalFine Inc.,制、平均粒径5μm)5.4质量份用上述双螺杆混炼挤出机、以200℃进行熔融混炼,从挤出机头挤出线料,冷却后造粒,从而得到树脂组合物(e2)。使用树脂组合物(e2)代替吸氧层(B2)用的树脂组合物(b2),除此之外,与实施例2同样地,得到具备层(E2)代替吸氧层(B2)的多层体。对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
(比较例3)
将聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC8001”)66.3质量份、铁粉(IPROS CORPORATION制商品名“海绵状铁粉”、平均粒径30μm)30.0质量份、氧化钙(CalFine Inc.,制、平均粒径5μm)2.5质量份和硅胶(Fuji Silysia Chemical Co.,Ltd.制商品名“Sylysia 710”)1.3质量份用上述双螺杆混炼挤出机、以200℃进行熔融混炼,从挤出机头挤出线料,冷却后造粒,从而得到树脂组合物(e3)。使用树脂组合物(e3)代替吸氧层(B2)用的树脂组合物(b2),除此之外,与实施例2同样地,得到具备层(E3)代替吸氧层(B2)的多层体。对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
(比较例4)
将聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC606”)95.5质量份和硅胶(Fuji Silysia Chemical Co.,Ltd.制商品名“Sylysia 710”)4.5质量份用上述双螺杆混炼挤出机、以200℃进行熔融混炼,从挤出机头挤出线料,冷却后造粒,从而得到树脂组合物(e4)。使用树脂组合物(e4)代替聚乙烯层(PE)用的聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC606”),除此之外,与实施例2同样地,得到具备层(E4)代替聚乙烯层(PE)的多层体。对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
(比较例5)
将聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC606”)91.0质量份和硅胶(Fuji Silysia Chemical Co.,Ltd.制商品名“Sylysia 710”)9.0质量份用上述双螺杆混炼挤出机、以200℃进行熔融混炼,从挤出机头挤出线料,冷却后造粒,从而得到树脂组合物(e5)。使用密封层(A2)用的聚乙烯(住友化学株式会社制商品名“SUMIKATHENE L705”)代替密封层(A1)用的离聚物(乙烯与甲基丙烯酸的共聚物的离聚物、金属离子的金属种类:钠、Du Pont-Mitsui Polychemicals Co.,Ltd.制商品名“HIMILAN 1601”),使用树脂组合物(e5)代替聚乙烯层(PE)用的聚乙烯(日本聚乙烯株式会社制商品名“Novatec LD:LC606”),除此之外,与实施例1同样地,得到具备密封层(A2)代替密封层(A1)、具备层(E5)代替聚乙烯层(PE)的多层体。对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
(比较例6)
将聚乙烯(日本聚乙烯株式会社制商品名”Novatec LD:LC606”)97.1质量份和氧化钙(CalFine Inc.,制、平均粒径5μm)2.9质量份用上述双螺杆混炼挤出机、以200℃进行熔融混炼,从挤出机头挤出线料,冷却后造粒,从而得到吸臭气层(C6)用的树脂组合物(c6)。
接着,分别从第2挤出机挤出上述树脂组合物(c6)、从第3挤出机挤出上述树脂组合物(b1),除此之外,与实施例2同样地得到3层薄膜。该3层薄膜的层构成从内层起为密封层(A2)(厚度20μm)/吸臭气层(C6)(厚度23μm)/吸氧层(B1)(厚度45μm)。在所得3层薄膜的吸氧层(B1)侧,以二氧化硅蒸镀面为粘接面,通过干层压粘接包含二氧化硅蒸镀聚对苯二甲酸乙二醇酯(TORAY ADVANCED FILM Co.,Ltd.制商品名“Barrialox”)的厚度12μm的氧阻隔层(D),得到多层体。
对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
(比较例7)
使用密封层(A2)用的聚乙烯(住友化学株式会社制商品名“SUMIKATHENE L705”)代替密封层(A1)用的离聚物(乙烯与甲基丙烯酸的共聚物的离聚物、金属离子的金属种类:钠、Du Pont-Mitsui Polychemicals Co.,Ltd.制商品名“HIMILAN 1601”),使用易氧化性热塑性树脂(Sealed Air公司制商品名“Cryovac(注册商标)OS Films”)代替吸氧层(B1)用的树脂组合物(b1),除此之外,与实施例3同样地,得到具备密封层(A2)代替密封层(A1)、具备易氧化性热塑性树脂层(EO)代替吸氧层(B1)的多层体。对于所得多层体,通过上述“多层体的评价方法1”和“多层体的评价方法2”进行评价。将结果与多层体的构成一并示于表1。
[表1]
本申请基于2016年12月9日申请的日本专利申请(特愿2016-239658),将其内容作为参照引入至此。
产业上的可利用性
根据本发明,可以提供具备优异的吸氧性的同时能够充分抑制臭气的多层体、使用该多层体的包装容器、和使用该包装容器的食品的保存方法。另外,根据本发明,可以提供封入食品并保管时、使臭气减少、且抑制来自外界气体的氧的透过从而能较高地维持食品的风味的多层体、使用该多层体的包装容器、和使用该包装容器的食品的保存方法。因此,本发明在要求这样的效果的领域、例如食品包装中有产业上的可利用性。
附图标记说明
(A)…密封层、(B)…吸氧层、(C)…吸臭气层、(D)…氧阻隔层、10…多层体、100…包装容器。

Claims (7)

1.一种多层体,其具备:含有热塑性树脂的密封层(A);含有热塑性树脂和铁粉的吸氧层(B);以及,具有氧阻隔性的氧阻隔层(D),且各层以前述的顺序进行层叠,
所述密封层(A)和所述吸氧层(B)中的至少一者含有离聚物作为所述热塑性树脂。
2.根据权利要求1所述的多层体,其中,在所述吸氧层(B)与所述氧阻隔层(D)之间还具备含有热塑性树脂和无机碱的吸臭气层(C)。
3.根据权利要求2所述的多层体,其中,所述无机碱为具有钙的无机碱。
4.一种包装容器,其以使含有热塑性树脂的密封层(A)为内侧、且使具有氧阻隔性的氧阻隔层(D)为外侧的方式具备权利要求1~3中任一项所述的多层体。
5.一种食品的保存方法,其通过权利要求4所述的包装容器封入食品并保存。
6.根据权利要求5所述的保存方法,其中,所述食品具有0.3以上且1.0以下的水分活度(Aw)。
7.根据权利要求5或6所述的保存方法,其中,所述食品为包含1质量%以上且50质量%以下的脂质的、巧克力点心和肉类中的任一者。
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