CN108291038B - 食品包装用膜和带包装盒的食品包装用卷膜 - Google Patents

食品包装用膜和带包装盒的食品包装用卷膜 Download PDF

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CN108291038B
CN108291038B CN201680069790.6A CN201680069790A CN108291038B CN 108291038 B CN108291038 B CN 108291038B CN 201680069790 A CN201680069790 A CN 201680069790A CN 108291038 B CN108291038 B CN 108291038B
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film
food packaging
mass
resin
acid
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CN108291038A (zh
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宫田裕幸
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Kitchen Expert Of Co ltd
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Showa Denko KK
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Abstract

本发明提供一种食品包装用膜，其含有热塑性树脂、蓝色着色剂、和聚甘油脂肪酸酯。

Description

食品包装用膜和带包装盒的食品包装用卷膜
技术领域
本发明涉及一种食品包装用膜和带包装盒的食品包装用卷膜。
背景技术
以往，食品包装用膜在饭店、餐厅等中用于业务，或者在家庭中在食品保存时、烹饪时等广泛使用。近年来，为了容易以目视辨别膜的碎片向食品中的混入，提出了一种将热塑性树脂作为主成分，且进一步含有铜酞菁系着色剂等着色剂的食品包装用膜(专利文献1)。
另一方面，在食品包装用膜中，为了防止食品中的水分以水滴的形式附着于膜，通常添加有防雾剂。
现有技术文献
专利文献
专利文献1：日本特开2015-7198号公报
发明内容
发明所要解决的课题
根据本发明人等的研究，判明：与蓝色着色剂一起使用防雾剂时，存在蓝色着色剂在膜中分散不均匀而导致膜的着色变得不均匀的情况。
因此，本发明的目的在于提供一种蓝色着色剂的分散性优异的食品包装用膜和带包装盒的食品包装用卷膜。
解决课题的手段
本发明提供一种食品包装用膜，其含有热塑性树脂、蓝色着色剂、和聚甘油脂肪酸酯。
以膜总量为基准计，聚甘油脂肪酸酯的含量优选为大于或等于0.5质量％。
热塑性树脂可以为选自由聚氯乙烯系树脂、聚偏二氯乙烯系树脂、聚烯烃系树脂、聚苯乙烯系树脂、聚酯系树脂和聚酰胺系树脂组成的组中的至少一种。
以膜总量为基准计，膜可以含有大于或等于70质量％的选自由聚氯乙烯系树脂、聚偏二氯乙烯系树脂和聚烯烃系树脂组成的组中的至少一种作为热塑性树脂。
另外，本发明提供一种带包装盒的食品包装用卷膜，其具备：上述食品包装用膜、卷绕有食品包装用膜的芯材、以及收纳有食品包装用膜和芯材的包装盒，并且在包装盒中设有用于切断食品包装用膜的刃部。
发明效果
根据本发明，能够提供一种蓝色着色剂的分散性优异的食品包装用膜和带包装盒的食品包装用卷膜。
附图说明
图1是表示带包装盒的食品包装用卷膜的示意图。
具体实施方式
本实施方式所涉及的膜含有热塑性树脂、蓝色着色剂、和聚甘油脂肪酸酯，适合用作食品包装用膜。
热塑性树脂可以为：聚氯乙烯等聚氯乙烯系树脂；聚偏二氯乙烯等聚偏二氯乙烯系树脂；聚乙烯、聚丙烯、乙烯-乙酸乙烯酯共聚物皂化物等聚烯烃系树脂；丁二烯-苯乙烯共聚物、丙烯腈-苯乙烯共聚物、聚苯乙烯、苯乙烯-丁二烯-苯乙烯共聚物、苯乙烯-异戊二烯-苯乙烯共聚物、苯乙烯-丙烯酸共聚物等聚苯乙烯系树脂；聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等聚酯系树脂；6-尼龙、6,6-尼龙、12-尼龙等聚酰胺系树脂等。从处理性优异的观点出发，热塑性树脂优选为聚氯乙烯系树脂、聚偏二氯乙烯系树脂或聚烯烃系树脂，更优选为聚氯乙烯系树脂、聚偏二氯乙烯系树脂或聚乙烯系树脂。从蓝色着色剂的分散性优异的观点出发，热塑性树脂优选为聚氯乙烯系树脂。
作为聚氯乙烯系树脂，从膜的成型性、耐热性和流动性优异的观点出发，优选平均聚合度为700～1300的聚氯乙烯系树脂。本说明书中的平均聚合度是指依照JIS K6720-2所测定的平均聚合度。
从机械特性优异的观点出发，聚氯乙烯系树脂可以为氯乙烯均聚物(聚氯乙烯树脂)，从赋予其他特性的目的出发，也可以为氯乙烯和可与其共聚的其他单体的共聚物。共聚物可以为接枝共聚物、嵌段共聚物或无规共聚物。作为其他单体的例子，可以列举：乙烯、丙烯、聚丁烯等烯烃；乙酸乙烯酯、月桂酸乙烯酯等饱和酸的乙烯基酯；丙烯酸甲酯、甲基丙烯酸甲酯等不饱和酸的烷基酯；月桂基乙烯基醚等烷基乙烯基醚；马来酸、丙烯腈、苯乙烯、甲基苯乙烯、偏二氟乙烯等。当聚氯乙烯系树脂为共聚物时，共聚物中的氯乙烯单元的含量以单体单元总量为基准计可以为大于或等于10质量％，从机械特性优异的观点出发，优选为大于或等于30质量％，更优选为大于或等于50质量％。共聚物中的氯乙烯单元的含量上限没有特别限定，例如以单体单元总量为基准计，可以为小于或等于99质量％。
聚氯乙烯系树脂例如可以为与丙烯腈-丁二烯-苯乙烯的三维聚合物等的聚合物混合物、利用醇等的后处理物、利用含氯化合物的后处理物。在这些情况下，以树脂总量为基准计，聚氯乙烯系树脂中的氯乙烯单元的含量可以为大于或等于10质量％。
聚偏二氯乙烯系树脂可以为偏二氯乙烯均聚物(聚偏二氯乙烯树脂)，也可以为例如包含偏二氯乙烯和可与偏二氯乙烯共聚的其他单体作为单体单元的共聚物。其他单体可以为氯乙烯、丙烯酸与碳原子数1～8的醇的丙烯酸酯、甲基丙烯酸与碳原子数1～8的醇的甲基丙烯酸酯、脂肪族羧酸的乙烯基酯、不饱和脂肪族羧酸、烯烃、乙烯基醚等。需要说明的是，偏二氯乙烯与氯乙烯的共聚物属于聚偏二氯乙烯系树脂。
从膜的成型性和耐热性的观点出发，以单体单元总量为基准计，聚偏二氯乙烯系树脂中的偏二氯乙烯单元的含量例如可以为大于或等于60质量％、大于或等于70质量％、或大于或等于80质量％。聚偏二氯乙烯系树脂中的偏二氯乙烯单元的含量上限没有特别限定，例如以单体单元总量为基准计，可以为小于或等于99质量％。偏二氯乙烯单元的含量可以利用核磁共振(NMR)装置进行测定。
聚偏二氯乙烯系树脂的重均分子量例如可以为40000～180000、60000～160000、或80000～140000。聚偏二氯乙烯系树脂的重均分子量可以利用GPC法，以分子量已知的聚苯乙烯作为标准物质来进行测定。
聚偏二氯乙烯系树脂的重均分子量测定中采用的GPC法的条件如下。使用Waters公司制造的凝胶色谱仪Alliance GPC2000型作为测定装置。以成为0.5重量％的方式使聚偏二氯乙烯系树脂溶解于四氢呋喃中，将所得的物质用作试样。
色谱柱：东曹株式会社制造的TSKgel GMHHR-H(S)HT 30cm×2、TSKgel GMH6-HTL30cm×2
流动相：四氢呋喃
检测器：示差折射计
流速：1.0mL/分钟
色谱柱温度：20℃
进样量：500μL
当热塑性树脂为聚氯乙烯系树脂或聚偏二氯乙烯系树脂时，膜可以进一步含有增塑剂。作为增塑剂，可以列举：环氧化亚麻籽油、环氧化大豆油、环氧化脂肪酸烷基酯等环氧化油；具有碳原子数6～10个的直链或支链烷基的己二酸酯、乙酰柠檬酸三丁酯、乙酰化三乙酯等羟基多元羧酸酯；癸二酸二正丁酯等脂肪酸族二元酸酯；季戊四醇酯、二乙二醇苯甲酸酯等二醇酯；磷酸三苯酯、磷酸三甲苯酯等磷酸酯；二乙酰单月桂酸甘油酯、氯化石蜡、聚酯系增塑剂等。这些增塑剂可以单独使用一种或者组合两种以上进行使用。增塑剂的含量可以根据所包装的食品的种类、包装形态、包装方法等用途，在相对于聚氯乙烯系树脂100质量份为例如20～50质量份的范围内适当调整。
作为聚烯烃系树脂，可以列举聚乙烯系树脂等，聚乙烯系树脂可以为低密度聚乙烯、线性低密度聚乙烯、线性超低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、以乙烯等作为单体单元的共聚物。具体而言，聚乙烯系树脂可以为乙烯与选自丙烯、1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-庚烯、1-辛烯等碳原子数3～10的α-烯烃、乙酸乙烯酯、丙酸乙烯酯等乙烯基酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯等不饱和羧酸酯、共轭二烯、非共轭二烯等不饱和化合物等的一种或两种以上的共聚物。以单体单元总量为基准计，聚乙烯系树脂中的乙烯单元的含量可以为大于或等于50质量％。
从生产率优异的观点出发，以膜总量为基准计，热塑性树脂的含量可以为大于或等于70质量％或大于或等于75质量％，另外，可以为小于或等于85质量％或小于或等于80质量％。优选聚氯乙烯系树脂、聚偏二氯乙烯系树脂或聚烯烃系树脂的含量为上述范围，更优选聚氯乙烯系树脂、聚偏二氯乙烯系树脂或聚乙烯系树脂的含量为上述范围。
蓝色着色剂例如为在可见光区域(380～750nm)中的最大吸收波长存在于600～750nm的着色剂。蓝色着色剂在可见光区域中的最大吸收波长下的吸光度为470nm下的吸光度的优选2倍以上、更优选3倍以上。具体而言，蓝色着色剂可以为铜酞菁(铜酞菁蓝)、六氰合铁(ii)酸铁(III)、氧化亚钴·氧化铝混合物、靛蓝、群青等。从分散性的观点出发，蓝色着色剂优选为铜酞菁。
以膜总量为基准计，蓝色着色剂的含量可以为大于或等于0.5质量％，另外，可以为小于或等于2.0质量％。
聚甘油脂肪酸酯为下述式(1)所表示的化合物。
[化1]
Figure BDA0001676964560000051
式(1)中，R1、R2和R3分别独立地表示氢原子或脂肪酸残基(烷基羰基)，且R1、R2和R3的至少一个表示脂肪酸残基(烷基羰基)。该脂肪酸残基(烷基羰基)的一部分可以被羟基等取代。n表示大于或等于3的整数。多个R2彼此可以相同也可以不同。
构成聚甘油脂肪酸酯的脂肪酸残基的碳原子数例如可以分别独立地为8～24。构成聚甘油脂肪酸酯的脂肪酸残基可以为饱和脂肪酸也可以为不饱和脂肪酸。作为构成聚甘油脂肪酸酯的脂肪酸残基的饱和脂肪酸，例如可列举辛酸、壬酸、癸酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、十七烷酸、硬脂酸、十九烷酸、花生酸、二十一烷酸、山嵛酸、二十三烷酸和二十四烷酸。作为构成聚甘油脂肪酸酯的脂肪酸残基的不饱和脂肪酸，例如可列举α-亚麻酸、十八碳四烯酸、二十碳五烯酸、二十二碳五烯酸、十二碳六烯酸、亚油酸、γ-亚麻酸、二高-γ-亚麻酸、花生四烯酸、二十二碳五烯酸、棕榈油酸、异油酸、二十碳烯酸(バウリン酸)、油酸、反油酸、芥酸和神经酸。这些饱和脂肪酸和不饱和脂肪酸的一部分可以被羟基等取代。作为脂肪酸的一部分被羟基取代后的化合物，例如可列举蓖麻醇酸、亚油酸、亚麻酸、鰶鱼酸和桐酸。
n可以为3～20的整数。聚甘油脂肪酸酯可以为n彼此不同的两种以上的聚甘油脂肪酸酯的混合物。
从蓝色着色剂的分散性更优异的观点出发，以膜总量为基准计，聚甘油脂肪酸酯的含量优选为大于或等于0.5质量％，更优选为大于或等于1.0质量％，进一步优选为大于或等于1.5质量％。以膜总量为基准计，聚甘油脂肪酸酯的含量可以为小于或等于2.5质量％、或小于或等于2.0质量％。
除了热塑性树脂、蓝色着色剂和聚甘油脂肪酸酯以外，膜还可以进一步含有其他成分。作为其他成分，可以列举热稳定剂、光稳定剂、除聚甘油脂肪酸酯以外的防雾剂、润滑剂、填充剂、抗析出剂、抗氧化剂、脱模剂、粘度降低剂、表面活性剂、除蓝色着色剂以外的着色剂、荧光剂、表面处理剂、交联剂、加工助剂、粘着剂、防静电剂、紫外线吸收剂、抗粘连剂等。
膜可以包含一层含有热塑性树脂、蓝色着色剂和聚甘油脂肪酸酯的层，也可以包含多层。当膜包含多层时，膜可以依次具备例如第一表面层、中间层和第二表面层。这种情况下，例如第一表面层和第二表面层可以含有热塑性树脂和聚甘油脂肪酸酯，中间层可以含有蓝色着色剂。例如，为了提高各层间的粘接性，膜可以进一步具备含有酸改性聚烯烃树脂等的粘接层，为了提高膜的耐热性，膜可以进一步具备含有聚酰胺系树脂的耐热层。当热塑性树脂为聚氯乙烯系树脂时，膜优选包含一层含有热塑性树脂(聚氯乙烯系树脂)、蓝色着色剂和聚甘油脂肪酸酯的层。
从高效地将食品与外部空气隔绝的观点出发，膜的厚度优选为大于或等于5μm，更优选为大于或等于6μm，另外，从处理性优异的观点出发，膜的厚度优选为小于或等于25μm，更优选为小于或等于12μm。
膜可以如下制造：使用V型搅拌器、螺带式搅拌器、亨舍尔混合机、高速混合机等混合机将含有热塑性树脂、蓝色着色剂和聚甘油脂肪酸酯的组合物混合，进一步根据需要使用混合辊、班伯里混合机、捏合机等混炼机进行混炼而得到组合物，之后例如进行挤出成型。具体而言，将该组合物供给至挤出机的料斗中，利用吹胀法、T模法等得到目标膜。通常，膜是一边制作一边卷绕的，将经卷绕的膜再重新卷绕成20m、50m等每个所期望的长度(成为卷状)，并装入至包装盒中，从而成为制品。即，本实施方式中的膜可以为食品包装用卷膜的形态，也可以为带包装盒的食品包装用卷膜的形态。
具体而言，如图1所示，带包装盒的食品包装用卷膜1可以为如下形态：具备食品包装用膜2、卷绕有食品包装用膜2的芯材3、以及收纳有食品包装用膜2和芯材3的包装盒4，并且在包装盒4中设有用于切断食品包装用膜2的刃部5。芯材3和包装盒4的材质没有特别限定。从容易从外部识别膜2的颜色的观点出发，优选包装盒4的至少一部分为透明、或者以不损害作为盒的功能的程度开设了孔。
当膜包含多层时，膜可以如下获得：将各层的构成原料分别投入至不同的挤出机中进行熔融挤出，利用吹胀、T模法等将各层共挤出并进行层叠。此时，优选将从T模挤出的熔融物直接利用铸造轧辊等一边急速冷却一边取回而形成膜。
对于以上述方式得到的膜，根据减轻热收缩率、自然收缩率等，抑制宽度收缩的产生等目的，可以进行加热辊间的纵向延伸、各种热固定、老化等热处理，为了赋予、促进防雾性、防静电性、粘着性等，也可以进行电晕处理，熟化等处理，印刷、涂布等表面处理和表面加工等。
以上所说明的膜是可从外部辨认经包装的食品的膜。另外，膜是具有延伸性(也称为伸缩性)的膜(拉伸膜)。
本实施方式所涉及的膜可以为用于食品分类的食品分类用膜。使用本实施方式所涉及的膜时，可以将两种以上的食品根据食品的种类分成至少两个组。即，例如可以用本实施方式所涉及的膜包装第一食品并分类为第一组，另一方面，用具有与本实施方式所涉及的膜不同颜色的膜或无色膜包装第二食品并分类为第二组。
具体而言，例如当存在包含第一过敏性物质的第一食品和包含第二过敏性物质的第二食品时，将第一食品分类为作为提供给对第一过敏性物质不具有过敏性症状的人的食品组的第一组，另一方面，将第二食品分类为作为提供给对第二过敏性物质不具有过敏性症状的人的食品组的第二组。在上述例子中，能够抑制将该过敏性物质提供给对第一过敏性物质或第二过敏性物质具有过敏性症状的人的事故的发生。
实施例
以下，基于实施例更具体地说明本发明，但本发明并不限定于实施例。
将表1、2中所示的热塑性树脂、蓝色着色剂、防雾剂和各种添加剂投入至高速混合机中，之后一边搅拌一边将材料温度从常温升至130℃并进行混合，之后在冷却至70℃的时间点取出，调制树脂组合物，使用安装有T模(宽度为350mm、间隙为0.4mm)的Φ40mm单螺杆挤出机(L/D＝20)，在树脂温度200℃将各树脂组合物挤出，制作厚度为8μm的膜。需要说明的是，表中的数值是固体成分换算的值，表示质量％。
热塑性树脂a1：聚氯乙烯系树脂(大洋聚氯乙烯株式会社制造，“TH-1000”，平均聚合度：1000)
热塑性树脂a2：聚乙烯系树脂(株式会社Prime Polymer制造，“NEO-ZEX0234N”)
蓝色着色剂b1：铜酞菁(铜酞菁蓝，大日精化工业株式会社制造，“NX-053Blue”)
防雾剂c1：聚甘油脂肪酸酯(理研维他命株式会社制造，“Poem PR-300”，聚甘油聚蓖麻油酸酯，式(1)中的n为4～6的混合物)
防雾剂c2：二甘油脂肪酸酯(理研维他命株式会社制造，“O-71-DE”，二甘油油酸酯)
防雾剂c3：甘油脂肪酸酯(理研维他命株式会社制造，“XO-100”，甘油单油酸酯)
防雾剂c4：脱水山梨糖醇脂肪酸酯(理研维他命株式会社制造，“L-250A”，脱水山梨糖醇月桂酸酯)
添加剂d1：己二酸二辛酯(新日本理化株式会社制造，“Sanso Cizer DOA”)
添加剂d2：环氧化大豆油(三和合成化学株式会社制造，“Chemicizer SE-100”)
添加剂d3：Ca/Zn系稳定剂(株式会社ADEKA制造，“SC-308E”)
(分散性的评价)
将所得的各膜切成20cm×20cm，制成试验片。通过目视观察该试验片，观察有无颜色不均，从而评价蓝色着色剂的分散性。评价基准如下所述。需要说明的是，如果评价为A、B或C，则可以说分散性优异。
A：试验片看不见颜色不均。
B：在试验片的1处可见颜色不均。
C：在试验片的2～3处可见颜色不均。
D：在试验片的4处以上可见颜色不均。
[表1]
Figure BDA0001676964560000091
[表2]
Figure BDA0001676964560000101
符号说明
1：带包装盒的食品包装用卷膜、2：食品包装用膜、3：芯材、4：包装盒、5：刃部。

Claims (4)

1.一种食品包装用膜，其含有热塑性树脂、蓝色着色剂、和聚甘油脂肪酸酯，
以膜总量为基准计，所述聚甘油脂肪酸酯的含量大于或等于0.5质量％且小于或等于2.5质量％，所述热塑性树脂的含量为大于或等于70质量％且小于或等于85质量％，所述蓝色着色剂的含量为大于或等于0.5质量％且小于或等于2.0质量％。
2.根据权利要求1所述的食品包装用膜，所述热塑性树脂为选自由聚氯乙烯系树脂、聚偏二氯乙烯系树脂、聚烯烃系树脂、聚苯乙烯系树脂、聚酯系树脂和聚酰胺系树脂组成的组中的至少一种。
3.根据权利要求1或2所述的食品包装用膜，以膜总量为基准计，含有大于或等于70质量％且小于或等于85质量％的选自由聚氯乙烯系树脂、聚偏二氯乙烯系树脂和聚烯烃系树脂组成的组中的至少一种作为所述热塑性树脂。
4.一种带包装盒的食品包装用卷膜，其具备：权利要求1～3中任一项所述的食品包装用膜、卷绕有所述食品包装用膜的芯材、以及收纳有所述食品包装用膜和所述芯材的包装盒，
在所述包装盒中设有用于切断所述食品包装用膜的刃部。
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