CN109563281B - 易撕裂性无拉伸树脂膜及使用其的包装材料用层叠膜 - Google Patents

易撕裂性无拉伸树脂膜及使用其的包装材料用层叠膜 Download PDF

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CN109563281B
CN109563281B CN201780045240.5A CN201780045240A CN109563281B CN 109563281 B CN109563281 B CN 109563281B CN 201780045240 A CN201780045240 A CN 201780045240A CN 109563281 B CN109563281 B CN 109563281B
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resin
film
polyethylene terephthalate
tear
easy
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CN109563281A (zh
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河村悟史
富田次郎
大泽誉史
太田芳弘
原拓也
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Toyo Seikan Group Holdings Ltd
Toyo Seikan Co Ltd
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Toyo Seikan Group Holdings Ltd
Toyo Seikan Co Ltd
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Abstract

本发明的目的在于，提供一种具有易撕裂性的树脂膜。一种易撕裂性无拉伸树脂膜，由聚对苯二甲酸乙二醇酯基树脂和与所述聚对苯二甲酸乙二醇酯基树脂的SP值的差为1.1～4.0(cal/cm3)0.5的第2树脂的混合物构成。提供一种在成为热密封面的内层膜20和由间苯二甲酸成分的共聚比率为0～5摩尔％的间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂构成的表层膜30之间具备该易撕裂性无拉伸树脂膜10的包装材料用层叠膜1B。

Description

易撕裂性无拉伸树脂膜及使用其的包装材料用层叠膜
技术领域
本发明涉及一种易撕裂性无拉伸树脂膜、及使用其的包装材料用层叠膜。
背景技术
目前，已知有作为填充各种药剂或食品等、通过热密封而进行密封的包装材料使用的树脂制的层叠膜。例如，(专利文献1)中公开有一种电灶加热用包装材料，其由以聚酯膜、具有阻隔层的聚酯膜、直线撕裂性聚酯膜、具有热密封性的聚烯烃膜的顺序层叠成的层叠膜构成。
另外，关于贴附剂、特别是在粘合剂层中含有药物的经皮吸收用贴附剂，目前，从保存中的品质保持等的观点出发，使用密闭性的包装材料进行密封包装。但是，存在如下问题：将在粘合剂中含有油状成分的贴附剂用包装材料进行包装时，由于贴附剂接触包装材料的内面而使油状成分吸附或转移至包装材料，粘合剂中的油状成分的含量发生变化，粘合特性发生变化。另外，在经皮吸收用贴附剂的情况下，含有的药物的经皮吸收性的降低或含有药物自身的吸附导致的药理效果的降低等问题被指出。针对这种问题，提出了由乙烯/乙烯醇共聚物或丙烯腈/丙烯酸甲酯共聚物形成包装材料的内面(专利文献2)。
但是，乙烯/乙烯醇共聚物或丙烯腈/丙烯酸甲酯共聚物价格高，因此谋求替代其的物质。对此，(专利文献3)中公开有一种包装材料，其由内层膜及基材膜构成，所述内层膜由具有热密封性的聚对苯二甲酸乙二醇酯基树脂构成，所述内层膜的热密封面由间苯二甲酸成分的共聚比率为10摩尔％～20摩尔％的间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂构成。上述(专利文献3)的包装材料防止在贴附剂的粘合剂中所含的油状成分吸附或转移至包装材料，同时具有优异的热密封特性。
现有技术文献
专利文献
专利文献1：日本特开2014-151945号公报
专利文献2：日本特开平5-305108号公报
专利文献3：日本特开2014-61663号公报。
发明内容
发明所要解决的技术问题
就包装材料用层叠膜而言，除上述热密封性等各种特性之外，在开封包装材料时具有良好的开封性(易撕裂性)也是重要的。上述(专利文献3)的包装材料的热密封性优异，但是其撕裂强度比较高，有待于改进。
因此，本发明的目的在于，提供一种例如适合作为构成上述(专利文献3)的包装材料的一层使用的、具有易撕裂性的树脂膜。另外，本发明的目的在于，提供一种利用上述的具有易撕裂性的树脂膜的包装材料用层叠膜。
用于解决问题的技术方案
本发明人等为了解决上述课题进行了深入研究，结果发现，通过无拉伸膜可解决课题，从而完成了发明，其中，所述无拉伸膜是将以聚对苯二甲酸乙二醇酯为主体的聚对苯二甲酸乙二醇酯基树脂和相对于上述聚对苯二甲酸乙二醇酯基树脂为非相溶的具有特定范围的SP值的差的树脂混合成的。即，本发明的要旨如下所述。
(1)一种易撕裂性无拉伸树脂膜，由聚对苯二甲酸乙二醇酯基树脂和与所述聚对苯二甲酸乙二醇酯基树脂的SP值的差为1.1～4.0(cal/cm3)0.5的第2树脂的混合物构成。
(2)根据上述(1)所述的易撕裂性无拉伸树脂膜，其中，聚对苯二甲酸乙二醇酯基树脂的比例为60重量％～80重量％，第2树脂的比例为40重量％～20重量％。
(3)根据上述(1)或(2)所述的易撕裂性无拉伸树脂膜，其中，第2树脂的Tg比聚对苯二甲酸乙二醇酯基树脂的Tg高25℃以上。
(4)根据上述(1)～(3)中任一项所述的易撕裂性无拉伸树脂膜，其中，第2树脂和聚对苯二甲酸乙二醇酯基树脂的270℃剪切速度121.6(1/秒)的熔体粘度比为0.3～1.6。
(5)根据上述(1)～(4)中任一项所述的易撕裂性无拉伸树脂膜，其中，第2树脂为环烯烃树脂或丙烯酸树脂。
(6)根据上述(1)～(5)中任一项所述的易撕裂性无拉伸树脂膜，其中，第2树脂在聚对苯二甲酸乙二醇酯基树脂中以粒子状分散，所述粒子的平均长宽比为1～5。
(7)根据上述(1)～(6)中任一项所述的易撕裂性无拉伸树脂膜，其中，长度方向及垂直方向的各自的撕裂强度为0.25N以下。
(8)一种包装材料用层叠膜，至少具有成为热密封面的内层膜和上述(1)～(7)中任一项所述的易撕裂性无拉伸树脂膜。
(9)一种包装材料用层叠膜，至少具有成为热密封面的内层膜、由间苯二甲酸成分的共聚比率为0～5摩尔％的间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂构成的表层膜、以及在所述内层膜及所述表层膜之间的上述(1)～(7)中任一项所述的易撕裂性无拉伸树脂膜。
(10)根据上述(8)或(9)所述的包装材料用层叠膜，其中，内层膜由间苯二甲酸成分的共聚比率为10摩尔％～20摩尔％的间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂构成。
本说明书包含成为本申请的优先权的基础的日本国专利申请号2016-142077号的公开内容。
发明效果
根据本发明，可以得到具有易撕裂性的树脂膜。目前为止无人知晓如本发明那样为无拉伸且具有易撕裂性的树脂膜。另外，根据本发明，可以使用上述的易撕裂性无拉伸树脂膜得到作为药剂或食品等的包装材料适合的层叠膜。
附图说明
图1是表示本发明的包装材料层叠膜的一个实施方式的剖面图。
图2是表示本发明的包装材料层叠膜的其它实施方式的剖面图。
具体实施方式
以下，详细地说明本发明。
本发明的树脂膜由聚对苯二甲酸乙二醇酯基树脂和第2树脂的混合物构成，为具有易撕裂性的无拉伸的树脂膜。聚对苯二甲酸乙二醇酯基树脂和第2树脂的特征在于，SP值的差在1.1～4.0(cal/cm3)0.5的范围内。由于SP值的差为1.1(cal/cm3)0.5以上，聚对苯二甲酸乙二醇酯基树脂和第2树脂成为非相溶状态，形成在聚对苯二甲酸乙二醇酯基树脂中分散有小滴状的第2树脂的状态而使膜的撕裂强度降低。另一方面，SP值的差超过4.0(cal/cm3)0.5的树脂在其膜的成形性方面是差的，不适合作为第2树脂。
构成本发明的易撕裂性无拉伸树脂膜的聚对苯二甲酸乙二醇酯基树脂是指以聚对苯二甲酸乙二醇酯为主体的聚酯均聚物或共聚物，具体而言，是指二羧酸成分及二醇成分的各自的单体的80摩尔％以上由对苯二甲酸及乙二醇构成的聚酯。作为对苯二甲酸以外的二羧酸成分，优选配合选自由间苯二甲酸(IA)、邻苯二甲酸、对β-氧基乙氧基苯甲酸、萘2,6-二羧酸、二苯氧基乙烷-4,4’-二羧酸、5-磺基间苯二甲酸钠、六氢对苯二甲酸、己二酸及癸二酸构成的组中的至少一种。作为二羧酸成分，更优选为添加有间苯二甲酸的共聚物，间苯二甲酸的添加量优选为二羧酸成分整体的1摩尔％～15摩尔％、特别为1摩尔％～5摩尔％。另外，作为其它的多元羧酸，可以含有微量的偏苯三酸或均苯四甲酸。
另外，二醇成分优选仅由乙二醇构成，但可以在不损害本发明的本质的范围内含有选自其以外的二醇成分例如丙二醇、1,4-丁二醇、二乙二醇、1,6-己二醇、环己烷二甲醇、双酚A的环氧乙烷加成物等中的一种或两种以上。
作为与聚对苯二甲酸乙二醇酯基树脂混合的第2树脂，只要与聚对苯二甲酸乙二醇酯基树脂的SP值(溶解度参数)的差为1.1～4.0(cal/cm3)0.5的范围内，就没有特别限定，可以从各种树脂中适当选择而使用。例如，由于聚对苯二甲酸乙二醇酯基树脂的SP值为12.4(cal/cm3)0.5，因此，作为第2树脂，可以举出例如选自聚丙烯酸乙酯(SP值：9.7)、聚丙烯酸丁酯(9.2)、聚丙烯腈(14.4)、聚异戊二烯(8.7)、聚偏二氯乙烯(11.2)、聚氯乙烯(11.0)、聚苯乙烯(10.6)、聚乙烯醇(16.0)、聚丁二烯(8.4)、聚甲基丙烯酸甲酯(9.9)、环烯烃树脂(COC：根据共聚比为10.0～10.4、COP：9.3)等中的一种以上。与聚对苯二甲酸乙二醇酯基树脂的SP值的差更优选为1.3～3.7(cal/cm3)0.5的范围内。
此外，本发明中的SP值是指使用由分子结构推算的Fedors的计算式算出的值。在Fedors的计算式中，对Tg超过25℃的化合物，也有根据最小重复单元中的主链骨架原子数而修正摩尔体积的方法，但在本发明中没有进行利用这种Tg的修正。
在上述中，在与聚对苯二甲酸乙二醇酯基树脂混合的情况下，膜的撕裂强度小，另外，容易形成无拉伸膜，因此，作为第2树脂，特别优选丙烯酸树脂及环烯烃树脂。丙烯酸树脂是丙烯酸酯或甲基丙烯酸酯的聚合物，如上所述可以使用聚丙烯酸甲酯、聚丙烯酸乙酯、聚丙烯酸丁酯、聚甲基丙烯酸甲酯等。另外，作为环烯烃树脂，可以举出例如环烯烃和非环状烯烃的加成共聚物(环烯烃共聚物、COC)、1种或2种以上的环烯烃的开环易位聚合物、将所述开环易位聚合物进行氢化而得到的聚合物(环烯烃聚合物、COP)等。作为环烯烃，可举出降冰片烯基烯烃、四环十二碳烯基烯烃、二环戊二烯基烯烃及其衍生物等。作为该衍生物，可举出例如利用烷基(优选碳原子数1～20)、亚烷基(优选碳原子数1～20)、芳烷基(优选碳原子数6～30)、环烷基(优选碳原子数3～30)、羟基、烷氧基(优选碳原子数1～10)、乙酰基、氰基、酰胺基、酰亚胺基、甲硅烷基、芳香环、醚键、酯键等的取代衍生物。
除以上之外，聚苯乙烯也可以作为第2树脂优选使用。
另外，选择第2树脂的情况下，优选第2树脂的Tg比聚对苯二甲酸乙二醇酯基树脂的Tg高25℃以上，特别优选高30℃以上。聚对苯二甲酸乙二醇酯基树脂和第2树脂的Tg的差较大时，在将混合物进行膜化时，第2树脂先进行固化，因此，聚对苯二甲酸乙二醇酯基树脂和第2树脂的界面的密合性降低，撕裂强度进一步降低。此外，Tg可以用差示扫描型热量计(DSC)、以升温速度10℃/min求出。
进而，第2树脂和聚对苯二甲酸乙二醇酯基树脂的270℃剪切速度121.6(1/秒)的熔体粘度比优选为0.3～1.6，其中，优选为0.8～1.5。通过使聚对苯二甲酸乙二醇酯基树脂和第2树脂的熔体粘度差减小、使熔体粘度比(分散相和熔体粘度/基质的熔体粘度、即第2树脂的熔体粘度/聚对苯二甲酸乙二醇酯基树脂的熔体粘度)接近于1，进行混合的情况的分散性升高，膜更容易开裂，因此优选。此外，上述的熔体粘度可以基于JIS K7199“利用热塑性塑料的毛细管流变仪的流动特性试验方法”求出。
通过将以上的聚对苯二甲酸乙二醇酯基树脂及第2树脂进行混合，通过挤出等公知的手段进行膜化，可以得到本发明的易撕裂性无拉伸树脂膜。具体而言，有如下方法：在将混合的聚对苯二甲酸乙二醇酯基树脂和第2树脂的薄片投入挤出机之前进行混合、将该混合薄片投入挤出机并进行熔融、混合的方法；或不使聚对苯二甲酸乙二醇酯基树脂的薄片和第2树脂的薄片混合，分别投入各自的挤出机而进行熔融，用这些各自的挤出机在将熔融的聚对苯二甲酸乙二醇酯基树脂和第2树脂从模具挤出之前进行混合而导入于模具的方法等，可以使用任一种方法。混炼温度也因第2树脂的种类而不同，但优选设为255℃以上且低于295℃，更优选为255℃以上且低于285℃。另外，混合物树脂的挤出机内的滞留时间优选设为5分钟～20分钟。
聚对苯二甲酸乙二醇酯基树脂和第2树脂的混合物的比例没有特别限定，将聚对苯二甲酸乙二醇酯基树脂的比例设为60重量％～80重量％、优选设为65重量％～75重量％、将第2树脂的比例设为40重量％～20重量％、优选设为35重量％～25重量％时，分散状态成为理想的状态，可以使膜的撕裂强度进一步降低。
另外，用显微镜观察得到的易撕裂性无拉伸树脂膜时，为在聚对苯二甲酸乙二醇酯基树脂中以粒子状分散有第2树脂的状态，第2树脂的粒子的膜平面内的平均长宽比(长轴/短轴)为1～5，优选为1～3，特别优选为1～2。通过第2树脂在膜的长度方向(MD方向)和垂直方向(TD方向)以大致相同程度的粒子形状(低长宽比)进行分散，可以使膜的撕裂强度不依赖于撕裂方向而进一步减小。此外，上述的平均长宽比如下求出：用显微镜观察膜的MD方向及TD方向的剖面，求出在其各自中随机地选择10个的第2树脂的粒子的膜的沿MD方向的平均长度和沿TD方向的平均长度，由它们的比求出平均长宽比。
通过以上的方法而得到的本发明的树脂膜为具有易撕裂性的无拉伸的树脂膜，优选长度方向及垂直方向的各自的撕裂强度为0.25N以下，优选为0.2N以下。但是，并不限定于此，可以根据膜的构成及用途而具有其以上的撕裂强度。此外，本发明中的撕裂强度是指：基于JIS K7128，利用裤形试验方法，使用拉伸试验机所测定的值。
本发明的易撕裂性无拉伸树脂膜的厚度可以根据膜的用途而适当设定，没有特别限定。例如可以设为1μm～30μm，优选设为2μm～25μm，更优选设为3μm～20μm。
接着，对使用有如上所述的易撕裂性无拉伸树脂膜的包装材料用层叠膜进行说明。图1中示出本发明的包装材料用层叠膜的一个实施方式。该包装材料用层叠膜1A由成为热密封面的内层膜20和上述的易撕裂性无拉伸树脂膜10构成。易撕裂性无拉伸树脂膜10的、与内层膜20层叠的侧相反侧的面上，可以根据需要进一步层叠后述的表层膜、或基材膜等一个以上的层，层叠膜的层数没有特别限定。另外，在易撕裂性无拉伸树脂膜10和内层膜20之间也可以适当具备粘合剂层等其它层。该包装材料用层叠膜1A作为包装材料，在内侧填充食品或贴附剂等药剂等，可以通过内层膜20的热密封进行密封而使用。作为层叠膜中的一层，具备易撕裂性无拉伸树脂膜10，因此，撕裂导致的开封变得容易。
作为内层膜20，只要具有热密封性即可，进而，优选根据密封的对象具有相对于耐药品性、油状成分的非吸附性。这种内层膜20的材质可以从各种树脂中适当选择，作为具体例，可以举出聚丙烯腈、聚对苯二甲酸乙二醇酯基树脂、环烯烃基树脂等。其中，间苯二甲酸成分的共聚比率为10摩尔％～20摩尔％的间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂，其热密封性优异，因此特别优选使用。此外，在此所说的间苯二甲酸成分的共聚比率是指二羧酸成分整体中间苯二甲酸所占的比例。
用作成为热密封面的内层膜20的、间苯二甲酸成分的共聚比率为10摩尔％～20摩尔％的间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂，其油状成分的非吸附性优异，同时具有优异的热密封性。因此，所述间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂适合作为构成可以防止贴附剂中的油状成分向包装材料的转移的包装材料的热密封面的材料。
在内层膜20中，可以在不损害热密封特性及非吸附性的范围内添加各种添加剂。作为添加剂，可举出：抗氧化剂、紫外线吸收剂、防水解剂、防霉剂、固化催化剂、增塑剂、颜料、填充剂、SiO2等润滑剂等。这些添加剂的添加量因添加剂的种类而不同，优选进行合计而在内层膜中设为0～10重量％的范围内。
内层膜20的厚度过厚时，层叠膜整体的撕裂性降低，相反其过薄时，存在热密封强度降低的倾向，因此，考虑它们的平衡而适当设定。例如，可以设为1μm～20μm、优选2μm～10μm、更优选3μm～8μm，但并不限定于此。
在制造包装材料用层叠膜1A时，可以使用现有公知的各种成形法。例如，可以适当采用以下方法：将构成易撕裂性无拉伸树脂膜10的混合物和构成内层膜20的树脂同时从多层T模具中共挤出而进行成膜的方法；或在预先制膜的内层膜20上将易撕裂性无拉伸树脂膜10进行熔融挤出而贴合的挤出层压法；或分别地制造易撕裂性无拉伸树脂膜10及内层膜20，经由粘合剂而使这些膜贴合的干式层压法等。将内层膜20进行成膜的情况下，作为其方法，可以使用T模具成形或吹塑成形等公知的成膜方法。此时，优选热熔融状态的膜通过迅速冷却而进行固化。通过迅速冷却，抑制树脂的结晶化，可得到热密封特性优异的膜。另外，内层膜20优选为以无拉伸或低倍率进行了拉伸的状态。内层膜20由聚对苯二甲酸乙二醇酯基树脂构成的情况下，有可能通过以高倍率进行拉伸而引起取向结晶化、热密封性降低。
在作为包装材料实际使用的情况下，可以在易撕裂性无拉伸树脂膜10上进一步设置基材膜等一个或更多个层。作为基材膜，没有特别限定，从透明性、印刷适性、耐药品性及强度优异方面考虑，可以使用双轴拉伸聚对苯二甲酸乙二醇酯、双轴拉伸聚酰胺、双轴拉伸聚丙烯的膜等。基材膜的厚度(除下述的阻气层之外)优选设为5μm～20μm，特别优选设为10μm～15μm。
进而，还优选以防止氧气和水蒸气的透过为目的，层叠阻气层。作为阻气层，可以使用铝箔等。铝箔不仅相对于氧气和水蒸气的阻隔性优异，而且遮光性也优异，可以优选使用。层叠阻气层的情况下，其厚度优选为2μm～20μm，特别优选为5μm～10μm的范围。
由包装材料用层叠膜1A及上述基材膜、阻气层等构成的包装材料可以通过制袋成三方或四方密封的通常的袋类、带插角袋(ガセット付パウチ)类、直立的袋类、枕形袋类等而制成包装袋。制袋可以使用公知的制袋法而进行。
用上述包装材料包装的贴附剂由支撑体和粘合剂层构成，可以在粘合剂层中配合药物，使药物进行经皮吸收而进行各种疾病的治疗或预防。在此所说的药物没有特别限定，也可以使用全身性作用药、局部作用药的任一种。作为这样的药物，可举出例如：肾上腺皮质类固醇剂、非类固醇性抗炎症剂、抗风湿剂、睡眠剂、抗精神病剂、抗抑郁剂、情绪稳定剂、精神刺激剂、抗焦虑剂、抗癫痫剂、偏头痛治疗剂、震颤性麻痹病治疗剂、蕈毒碱受体拮抗剂、多动腿综合征治疗剂、脑循环·代谢改善剂、抗痴呆病剂、自律神经作用剂、肌弛缓剂、降压剂、利尿剂、血糖降下剂、高脂血症治疗剂、痛风治疗剂、全身麻醉剂、局部麻醉剂、抗菌剂、抗真菌剂、抗病毒剂、抗寄生虫剂、维生素剂、狭心症治疗剂、血管扩张剂、抗脉律不齐剂、抗组胺剂、中介物游离抑制剂(Mediator release inhibitor)、白三烯拮抗剂性激素剂、甲状腺激素剂、抗甲状腺剂、抗肿瘤剂、制吐剂、镇晕剂、气管支扩张剂、镇咳剂、去痰剂、戒烟辅助剂、抗骨质疏松症剂等。这些药物可以以游离体的形态使用，也可以以盐的形态使用。另外，这些药物可以单独使用或将2种以上混合而使用。
作为支撑体，只要在贴附时没有显著的不适感，就没有特别限定。具体而言，可举出：由聚酯、聚乙烯或聚丙烯等聚烯烃、聚氯乙烯、可塑化聚氯乙烯、可塑化醋酸乙烯酯-氯乙烯共聚物、聚氯乙烯、乙烯-醋酸乙烯酯共聚物、醋酸纤维素、乙基纤维素、乙烯-丙烯酸乙酯共聚物、聚四氟乙烯、聚氨酯、离聚物树脂等合成树脂构成的单独膜、或它们的层压膜、或橡胶制、上述合成树脂制、聚对苯二甲酸乙二醇酯等聚酯制、或尼龙等聚酰胺制的多孔性膜或片材、无纺布、织物或这些和上述合成树脂膜的层压物等。
贴附剂优选为经皮吸收制剂、且将含有经皮吸收性药物的粘合剂层在支撑体的一面形成而成的物质。另外，也可以在该粘合剂层的另一个面层叠进行了剥离处理的离形膜。
作为贴附剂的形态，为平面上的扁平的形态，平面形状除大致矩形之外，可举出三角形、五角形等多角形、即以大致直线形成轮廓的形状、或以椭圆、圆形等曲线形成轮廓的形状、它们的组合等，但并不限定于这些。
贴附剂的大小可以根据贴附剂的用途和适用处等而适当选择。例如，贴附剂的形状为大致矩形的情况下，一般而言，其一边的长度为15mm～90mm，另一边的长度也为15mm～90mm。
贴附剂的总厚度通常为50μm～2000μm，优选为100μm～1000μm的范围。另外，贴附剂由支撑体和粘合剂层构成，但支撑体的厚度通常为1μm～1000μm，粘合剂层通常为10μm～200μm，优选为15μm～150μm。
粘合剂层可以含有油状成分。为了将粘合剂层进行可塑化并赋予柔软感而使皮肤刺激性减少、或调整药物的经皮吸收性而使用所含有的油状成分。油状成分优选在室温(25℃)下为液状的物质、或在将2种以上混合使用的情况下、最终混合物在室温(25℃)下成为液状的物质。作为这种油状成分，可举出例如：油醇、辛基十二烷醇等高级醇；甘油、乙二醇、聚丙二醇等多元醇；辛酸、油酸等高级脂肪酸；十四烷酸异丙酯、棕榈酸异丙酯、油酸乙酯等脂肪酸酯；癸二酸二乙酯、己二酸二异丙酯等多元酸酯；三异硬脂酸二甘油酯(Diglyceryltriisostearate)、脱水山梨糖醇单油酸酯、丙二醇二辛酸酯、聚乙二醇单月桂酸酯、四油酸聚氧乙烯山梨糖醇等多元醇脂肪酸酯；聚氧乙烯月桂基醚等聚氧乙烯烷基醚；角鲨烷、液体石蜡等烃；橄榄油、蓖麻油等植物油；硅油；N-甲基吡咯烷酮、N-十二烷基吡咯烷酮之类的吡咯烷酮类；癸基甲基亚砜之类的亚砜类等。这些油状成分可以单独使用，或2种以上混合而使用。
就本发明中的贴附剂用的包装袋的形状而言，只要是可以包装贴附剂的形状，就没有特别限定，例如除正方形、长方形等大致矩形之外，可举出三角形、五角形等多角形、圆形、椭圆形、其它的图形等。另外，贴附剂用的包装袋的形状和所包装的贴附剂的形状只要可以进行贴附剂的个别包装(密封)，则可以相同，也可以为不同的形状。
接着，将本发明的包装材料用层叠膜的其它实施方式示于图2。图2的包装材料用层叠膜1B具有：成为热密封面的内层膜20、表层膜30、和在这些内层膜20及表层膜30之间的易撕裂性无拉伸树脂膜10。
表层膜30可以由树脂等构成，优选具有耐热性、耐药品性、非吸附性等特性。作为这种表层膜30的材质，可以举出聚丙烯腈、聚对苯二甲酸乙二醇酯基树脂、环烯烃基树脂等。其中，间苯二甲酸成分的共聚比率为0～5摩尔％的间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂相对于油状成分具有高的非吸附性，因此优选使用。上述的低改性率的聚对苯二甲酸乙二醇酯作为聚酯瓶用材料通用且大量地被使用，因此，可以廉价地提供，经济性优异。
如图2所示，设置表层膜30的情况下，其厚度没有特别限定，例如优选设为1μm～20μm。
在制造包装材料用层叠膜1B时，可以通过公知的方法进行制膜，例如，可以通过将表层膜30、易撕裂性无拉伸树脂膜10及内层膜20的3层同时从多层T模具中共挤出而进行成膜的方法、在表层膜30及内层膜20之间将易撕裂性无拉伸树脂膜进行熔融挤出并贴合的挤出层压法、或分别地制作表层膜30、易撕裂性无拉伸树脂膜10及内层膜20的3层、经由粘合剂将这些层贴合的干式层压法等来制造。
与图1所示的实施方式同样地，也可以在包装材料用层叠膜1B上进一步层叠基材膜或阻气层等，制成实际使用的包装材料。关于这些各层的构成，按照图1的实施方式。
实施例
以下，基于实施例及比较例，进一步详细地说明本发明，但本发明并不限定于这些实施例。
(易撕裂性无拉伸树脂膜的制造及撕裂试验)
将易撕裂性无拉伸树脂膜的制造中使用的材料示于表1。表1中的各符号的意思如下所述。
PET/IA2：间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂(间苯二甲酸成分的共聚比率：2摩尔％)
PMMA：聚甲基丙烯酸甲酯
COC：环烯烃共聚物(乙烯和降冰片烯的共聚物，表中的括号内表示共聚比(重量％))
PEN：聚萘二甲酸乙二醇酯
PP：聚丙烯
PS：聚苯乙烯
EVOH：乙烯·醋酸乙烯酯共聚物皂化物(表中的括号内表示共聚比(摩尔％))
Tg：玻璃化转变温度(℃)
熔体粘度：270℃剪切速度121.6(1/秒)的值(Pa·s)
[表1]
Figure BDA0001952025030000121
熔体粘度比＝(分散相的熔体粘度/基质的熔体粘度)
对于表1所示的各材料，在表2所示的各膜构成中使用挤出机进行混炼、挤出，制造出目标树脂膜。挤出成形温度设为270℃。得到的树脂膜的厚度为20μm。关于制造的各树脂膜，在以下的条件下实施撕裂试验。将其结果示于表2。表2中，MD表示纵向(流动方向)，TD表示垂直方向的撕裂强度。
试验方法：裤形试验方法
试验片：裤形试验片(纵：150mm、横：50mm、狭缝长度：75mm)
试验条件：试验速度200mm/分钟、测定温度25℃(室温)
[表2]
Figure BDA0001952025030000131
如表2所示，作为第2树脂，使用有与PET/IA2的SP值的差为1.1～4.0(cal/cm3)0.5的范围内的树脂的实施例1～5、及实施例19～22的树脂膜与和SP值的差小的PEN、及SP值的差大的PP进行混合的情况相比，撕裂强度均小，作为易撕裂性的树脂膜具有良好的特性。但是，第2树脂的比例为50重量％的实施例3，膜的成形性不稳定。
(包装材料用层叠膜的制造及撕裂试验)
接着，制造图2所示的3层结构的包装材料用层叠膜，进行撕裂试验。层叠膜的制造中使用的材料除内层膜之外，与表1相同。在内层膜中，使用间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂(间苯二甲酸成分的共聚比率15摩尔％、PET/IA15)。
表层膜由PET/IA2单体构成，成为热密封面的内层膜是在PET/IA15中添加平均粒径2.5μm的球状二氧化硅作为润滑剂而构成(添加量为内层膜整体的10重量％)。夹持于表层膜及内层膜的易撕裂性无拉伸树脂膜(芯层)由表3所示的各混合物构成。在制造层叠膜时，通过将3层同时从多层T模具中共挤出并进行成膜而进行。得到的层叠膜的厚度为17μm(层比为表层：芯层：内层＝3.6：9.8：3.6)。作为比较例7，将仅由表层膜和内层膜构成的2层构成的膜以与含有芯层的层叠膜相同的厚度17μm(层比为表层：内层＝13.4：3.6)进行成膜。
对制造的实施例6～18及比较例7的包装材料用层叠膜，在以下的条件下实施撕裂试验。将其结果示于表3。
试验方法：裤形试验方法
试验片：裤形试验片(纵：150mm、横：50mm、狭缝长度：75mm)
试验条件：试验速度200mm/分钟、测定温度25℃(室温)
[表3]
Figure BDA0001952025030000141
如表3所示，在使用本发明的易撕裂性无拉伸树脂膜作为芯层的情况下，即使作为层叠膜整体，也均可以实现低的撕裂强度。熔体粘度比为0.3～1.6的范围外的实施例6、7及13、或第2树脂的Tg低的实施例12与其以外的实施例相比，撕裂强度升高一些，但与比较例相比时，为充分低的值。进而，对实施例14及实施例16，显微镜观察了制造的层叠膜的剖面的结果，观察到第2树脂的粒子分散于PET/IA2中的状态。就粒子的平均长宽比而言，用显微镜观察MD方向及TD方向的剖面，求出在其各自中随机地选择了10个的第2树脂的粒子的膜的沿MD方向的平均长度和沿TD方向的平均长度，算出它们的比而设为平均长宽比。将测定的结果示于表4。
[表4]
Figure BDA0001952025030000151
(参考例：进一步多层化的膜的撕裂性评价)
作为参考例2～7，在上述实施例8～11及17以及比较例7的包装材料用层叠膜(厚度17μm)上进一步依次层叠粘合剂层、7μm铝箔、粘合剂层及12μm拉伸PET膜。参考例1中，取代参考例2～7中的包装材料用层叠膜，为使聚丙烯腈膜进行层叠的膜。对得到的层叠体，在以下的条件下实施撕裂试验。将其结果示于表5。
试验方法：裤形试验法
试验片：裤形试验片(100mm×100mm的4方密封平袋、狭缝长度10mm)
试验条件：试验速度200mm/分钟、测定环境23℃-50％RH
n数：10
[表5]
Figure BDA0001952025030000152
Figure BDA0001952025030000161
如表5所示，在构成层叠体的一层中使用有本发明的包装材料用层叠膜的参考例3～7，显示与层叠有PAN膜的参考例1同程度的易撕裂性，显示可替代为高价的PAN膜。
符号说明
1A、1B包装材料用层叠膜
10易撕裂性无拉伸树脂膜
20内层膜
30表层膜
本说明书中引用的全部的出版物、专利及专利申请通过直接引用而被引入于本说明书中。

Claims (8)

1.一种易撕裂性无拉伸树脂膜，由聚对苯二甲酸乙二醇酯基树脂和与所述聚对苯二甲酸乙二醇酯基树脂的SP值的差为1.1～4.0(cal/cm3)0.5的第2树脂的混合物构成；
其中，第2树脂在聚对苯二甲酸乙二醇酯基树脂中以粒子状分散，所述粒子的平均长宽比为1～2；并且
其中，长度方向及垂直方向的各自的撕裂强度为0.25N以下。
2.根据权利要求1所述的易撕裂性无拉伸树脂膜，其中，
聚对苯二甲酸乙二醇酯基树脂的比例为60重量％～80重量％，第2树脂的比例为40重量％～20重量％。
3.根据权利要求1或2所述的易撕裂性无拉伸树脂膜，其中，
第2树脂的Tg比聚对苯二甲酸乙二醇酯基树脂的Tg高25℃以上。
4.根据权利要求1或2所述的易撕裂性无拉伸树脂膜，其中，
第2树脂和聚对苯二甲酸乙二醇酯基树脂的、270℃剪切速度121.6(1/秒)的熔体粘度比为0.3～1.6。
5.根据权利要求1或2所述的易撕裂性无拉伸树脂膜，其中，
第2树脂为环烯烃树脂或丙烯酸树脂。
6.一种包装材料用层叠膜，至少具有成为热密封面的内层膜和权利要求1～5中任一项所述的易撕裂性无拉伸树脂膜。
7.一种包装材料用层叠膜，至少具有成为热密封面的内层膜、由间苯二甲酸成分的共聚比率为0～5摩尔％的间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂构成的表层膜、以及在所述内层膜及所述表层膜之间的权利要求1～5中任一项所述的易撕裂性无拉伸树脂膜。
8.根据权利要求6或7所述的包装材料用层叠膜，其中，
内层膜由间苯二甲酸成分的共聚比率为10摩尔％～20摩尔％的间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂构成。
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