CN108291040B - 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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CN108291040B
CN108291040B CN201680069821.8A CN201680069821A CN108291040B CN 108291040 B CN108291040 B CN 108291040B CN 201680069821 A CN201680069821 A CN 201680069821A CN 108291040 B CN108291040 B CN 108291040B
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film
mass
food packaging
food
resin
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CN108291040A (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、和白色着色剂。

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。为了提高使用时的便利性，对食品包装用膜进行了各种改良。例如专利文献1中，以防止被包装的食材和容器与膜的同化，并且可容易地辨别膜的端面，且防止该端面处的膜彼此、或食材和容器与膜的过度密合等为目的，公开了一种对膜的预定部位实施压纹加工而成的食品包装用膜。
现有技术文献
专利文献
专利文献1：日本特开2003-63555号公报
发明内容
发明所要解决的课题
本发明的目的在于提供一种即使在混入至食品中时也可识别、且制膜性和生产率优异的食品包装用膜以及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、和白色着色剂。
以膜总量为基准计，蓝色着色剂的含量优选为0.45～2.2质量％。
以膜总量为基准计，白色着色剂的含量优选为0.15～0.55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。
膜可以为可从外部辨认经包装的食品的膜。
膜的全光线透过率可大于或等于70％。
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，能够提供一种即使在混入至食品中时也可识别、且制膜性和生产率优异的食品包装用膜以及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、和白色着色剂，可适宜地用作食品包装用膜。
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。
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据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，可以为氯乙烯和可与其进行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，以单体单元总量为基准计，共聚物中的氯乙烯单元的含量可以为大于或等于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的上限没有特别限定，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掺合物、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)，例如可以为含有偏二氯乙烯、和可与偏二氯乙烯进行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、丙烯酸与碳数1～8的醇的丙烯酸酯、甲基丙烯酸与碳数1～8的醇的甲基丙烯酸酯、脂肪族羧酸的乙烯酯、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的上限没有特别限定，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通过核磁共振(NMR)装置来测定。
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通过GPC法，将分子量已知的聚苯乙烯作为标准物质来测定。
用于聚偏二氯乙烯系树脂的重均分子量测定的GPC法的条件如下所述。作为测定装置，使用Waters公司制造的凝胶色谱仪Alliance GPC2000型。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，膜可进一步含有增塑剂。作为增塑剂，可列举：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，具有碳数6～10个的直链或支链烷基的己二酸酯、乙酰基柠檬酸三丁酯、乙酰基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，甘油二乙酰单月桂酸酯，氯化石蜡，聚酯系增塑剂等。这些增塑剂可单独使用一种、或将两种以上组合使用。增塑剂的含量可以根据被包装的食品的种类、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质量份的范围内适宜调整。
作为聚烯烃系树脂，可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、将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中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。
从识别性更优异的观点出发，以膜总量为基准计，蓝色着色剂的含量优选为大于或等于0.45质量％，更优选为大于或等于0.6质量％，进一步优选为大于或等于0.75质量％，特别优选为大于或等于1.0质量％。从制膜性和生产率更优异的观点出发，以膜总量为基准计，蓝色着色剂的含量优选为小于或等于2.2质量％，更优选为小于或等于2.0质量％，进一步优选为小于或等于1.9质量％，特别优选为小于或等于1.8质量％。从识别性、制膜性和生产率全部更优异的观点出发，以膜总量为基准计，蓝色着色剂的含量优选为0.45～2.2质量％、0.45～2.0质量％、0.45～1.9质量％、0.45～1.8质量％、0.6～2.2质量％、0.6～2.0质量％、0.6～1.9质量％、0.6～1.8质量％、0.75～2.2质量％、0.75～2.0质量％、0.75～1.9质量％、0.75～1.8质量％、1.0～2.2质量％、1.0～2.0质量％、1.0～1.9质量％、或1.0～1.8质量％。蓝色着色剂的含量优选多于后述的白色着色剂的含量。
白色着色剂例如是在可见光区域(380～750nm)的整个范围内的吸光度小于或等于0.3(使可见光线散射)的着色剂。具体而言，白色着色剂可以为氧化钛、氧化钛-硫酸钡、氧化钛-硅酸镁、氧化钛-硫酸钙、氧化锌。
从识别性更优异的观点出发，以膜总量为基准计，白色着色剂的含量优选为大于或等于0.15质量％，更优选为大于或等于0.2质量％，进一步优选为大于或等于0.25质量％，特别优选为大于或等于0.3质量％。从制膜性和生产率更优异的观点出发，以膜总量为基准计，白色着色剂的含量优选为小于或等于0.55质量％，更优选为小于或等于0.5质量％，进一步优选为小于或等于0.45质量％，特别优选为小于或等于0.4质量％。从识别性、制膜性和生产率全部更优异的观点出发，以膜总量为基准计，白色着色剂的含量优选为0.15～0.55质量％、0.15～0.5质量％、0.15～0.45质量％、0.15～0.4质量％、0.2～0.55质量％、0.2～0.5质量％、0.2～0.45质量％、0.2～0.4质量％、0.25～0.55质量％、0.25～0.5质量％、0.25～0.45质量％、0.25～0.4质量％、0.3～0.55质量％、0.3～0.50质量％、0.3～0.45质量％、或0.3～0.4质量％。
除热塑性树脂、蓝色着色剂和白色着色剂以外，膜可进一步含有其他成分。作为其他成分，可列举：防雾剂、热稳定剂、光稳定剂、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、除蓝色着色剂和白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、抗静电剂、紫外线吸收剂、抗粘连剂等。
膜可包含一层含有热塑性树脂、蓝色着色剂和白色着色剂的层，也可包含多层。当膜包含多层时，膜可依次具备例如第一表面层、中间层、和第二表面层。在该情况下，例如中间层可以含有蓝色着色剂和白色着色剂。例如，为了提高各层间的粘接性，膜可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，优选为小于或等于25μm，更优选为小于或等于12μm。
从食品的辨认性优异的观点出发，膜的全光线透过率优选为大于或等于70％，更优选为大于或等于75％。从对于食品的识别性更优异的观点出发，膜的全光线透过率优选为小于或等于85％，更优选为小于或等于80％，进一步优选为小于或等于79％。膜的全光线透过率是基于依据JIS K7361-1所测定的全透过光量，根据下述式算出的。
全光线透过率(％)＝(全透过光量)/(入射光量)×100
膜通过如下方式来制造：利用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、蓝色着色剂和白色着色剂的组合物混合，进一步根据需要利用混合辊、班布里混合机、捏合机等混炼机进行混炼，从而获得组合物后，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模法等获得目标膜。通常，膜是一边制作一边卷绕的，将经卷绕的膜进一步重新卷绕成20m、50m等各个所期望的长度(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，膜通过如下方式获得：将各层的构成原料分别投入至不同的挤出机中并熔融挤出，通过吹胀、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、抗静电性、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，膜为具有延伸性(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。如果使用本实施方式所涉及的膜，则可根据食品的种类将两种以上的食品分成至少两个组。即，例如可利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，利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，例如当存在含有第一过敏性物质的第一食品和含有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于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于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于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。
<实施例1～6和比较例1～4>
将表1、2中所示的热塑性树脂、蓝色着色剂、白色着色剂和各种添加剂投入至高速混合机中后，一边进行搅拌一边将材料温度从常温升温至130℃，混合后，在冷却至70℃的时间点取出而调制树脂组合物，利用安装有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，表中的数值为固体成分换算的值，表示质量％。
<实施例7～15和比较例5～6>
使用表3、4中所示的以下的热塑性树脂、蓝色着色剂、白色着色剂和各种添加剂来调制树脂组合物，并利用吹胀制膜装置将各树脂组合物挤出，从而制作厚度为9μm的膜。需要说明的是，表中的数值为固体成分换算的值，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”)
偏二氯乙烯系树脂a3：偏二氯乙烯与氯乙烯的共聚物(偏二氯乙烯/氯乙烯(质量比)＝90/10)，重均分子量：80000
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”)
白色着色剂c1：氧化钛(堺化学工业株式会社制造，“FTR-700”)
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，“ChemicizerSE-100”)
添加剂d3：甘油脂肪酸酯(理研维他命株式会社制造，“XO-100”)
添加剂d4：Ca/Zn系稳定剂(株式会社ADEKA制造，“SC-308E”)
添加剂d5：癸二酸二丁酯(丰国制油株式会社制造，“DBS”)
添加剂d6：乙酰基柠檬酸三丁酯(旭化成精细化工株式会社制造，“ATBC”)
如以下所示，对所获得的各膜实施全光线透过率的测定和相对于食品的识别性的评价。将结果示于表1～4中。
(全光线透过率的测定)
利用日本电色工业公司制造的雾度计(型号：NDH5000)，依据JIS K7361-1测定膜的全透过光量，并根据下述式计算膜的全光线透过率。
全光线透过率(％)＝(全透过光量)/(入射光量)×100
(识别性的评价)
从所获得的膜制作3mm～10mm见方的碎片，当使膜混入至食品中时，以目视观察是否能够识别膜的碎片。评价基准如下所述。需要说明的是，如果评价为A或B，则可以说识别性优异。
A：相对于食品，极其容易识别膜。
B：相对于食品，容易识别膜。
C：相对于食品，难以识别膜。
(制膜性的评价)
利用T模挤出机，在树脂温度200℃将各树脂组合物挤出而进行膜的成型，并观察所获得的膜的外观，从而评价制膜性。评价基准如下所述。需要说明的是，如果评价为A或B，则可以说制膜性优异。
A：可获得厚度大致均匀的膜，在24小时的挤出中未产生黄变。
B：膜的厚度略微可见不均，在24小时的挤出中产生了黄变。
C：膜的厚度不均严重，在8小时的挤出中产生了黄变。
(生产率的评价)
对使用T模挤出机在树脂温度200℃将各树脂组合物挤出而进行膜的成型时所产生的生产故障(开孔、膜断开和狭缝不良状况)的每24小时的产生次数进行计数，从而评价生产率。评价基准如下所述。需要说明的是，如果评价为A或B，则可以说生产率优异。
A：生产故障次数为0～2次
B：生产故障次数为3～4次
C：生产故障次数大于或等于5次
[表1]
Figure BDA0001677254390000101
[表2]
Figure BDA0001677254390000102
[表3]
Figure BDA0001677254390000111
[表4]
Figure BDA0001677254390000112
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 (7)

1.一种食品包装用膜，其含有：热塑性树脂、蓝色着色剂、和白色着色剂，以膜总量为基准计，所述白色着色剂的含量为0.15～0.55质量％。
2.根据权利要求1所述的食品包装用膜，以膜总量为基准计，所述蓝色着色剂的含量为0.45～2.2质量％。
3.根据权利要求1或2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、聚酯系树脂和聚酰胺系树脂组成的组中的至少一种。
4.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％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。
5.根据权利要求1或2所述的食品包装用膜，所述膜为可从外部辨认经包装的食品的膜。
6.根据权利要求1或2所述的食品包装用膜，所述膜的全光线透过率大于或等于70％。
7.一种带包装盒的食品包装用卷膜，其具备：权利要求1～6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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