CN113412184A - 双轴拉伸聚酯膜 - Google Patents
双轴拉伸聚酯膜 Download PDFInfo
- Publication number
- CN113412184A CN113412184A CN202080013603.9A CN202080013603A CN113412184A CN 113412184 A CN113412184 A CN 113412184A CN 202080013603 A CN202080013603 A CN 202080013603A CN 113412184 A CN113412184 A CN 113412184A
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- Prior art keywords
- film
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- polyester
- polyester film
- biaxially stretched
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- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
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- 229910052787 antimony Inorganic materials 0.000 claims abstract description 21
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920000728 polyester Polymers 0.000 claims description 40
- 229920001225 polyester resin Polymers 0.000 claims description 23
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Abstract
提供一种双轴拉伸聚酯膜,其锑含量极低,卫生性优异,另外异物少,具有优异的透明性、耐热性,并且印刷性、加工性、生产率良好。所述双轴拉伸聚酯膜中,膜中的锑的含量为10ppm以下,磷的含量为25ppm以上且75ppm以下,膜的特性粘度为0.51dl/g以上且0.70dl/g以下,且每1000平方米膜中1mm以上的缺陷数为1.0个以下。
Description
技术领域
本发明涉及卫生性优异、印刷性、加工性、生产率良好的双轴拉伸聚酯膜。
背景技术
作为耐热性、机械物性优异的热塑性树脂的聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)等聚酯树脂在塑料膜、电子学、能源、包装材料、汽车等非常多的领域中被利用。塑料膜中,双轴拉伸PET膜由于机械特性强度、耐热性、尺寸稳定性、耐化学药品性、光学特性等与成本的平衡优异,因此在工业用、包装用领域中被广泛使用。
在工业用膜的领域中,由于具有优异的透明性,所以可以用作面向液晶显示器、等离子体显示器等平板显示器(FPD)的功能膜。另外,赋予了耐水解性的PET膜也被用作太阳能电池背板用膜,作为功能性膜、基膜以各种目的使用。
在包装用膜的领域中,被用作食品包装用、阻气膜用途。特别是,阻气性优异的膜被用作食品、医药品、电子部件等的要求气密性的包装材料、或气体阻隔材料,近年来需求提高。
但是,包装用膜与食品直接接触,因此,从卫生性的方面出发,期望聚酯膜的异物少。另外,生产(聚合)聚酯的原料的工序中使用的锑催化剂有致癌性的可能性,因此,期望在聚酯膜中尽可能少或者不含锑。
以往,例如专利文献1、2中记载的那样,有不使用锑催化剂的聚酯原料。但是,对于使膜中的异物数降低的方法、期望的膜特性,并没有记载。
现有技术文献
专利文献
专利文献1:日本专利3461175号公报
专利文献2:日本专利3506236号公报
发明内容
发明要解决的课题
本发明的课题在于提供锑含量极少,另外异物也少,具有优异的透明性、耐热性,并且印刷加工适应性和印刷外观也优异的双轴拉伸聚酯膜和将该膜卷绕而成的膜卷的制造方法。
用于解决课题的手段
解决上述课题而成的本发明包括以下构成。
1.一种双轴拉伸聚酯膜,其特征在于,满足下述要件(1)~(4)。
(1)膜中的锑的含量为10ppm以下
(2)膜中的磷的含量为25ppm以上且75ppm以下
(3)膜的特性粘度为0.51dl/g以上且0.70dl/g以下
(4)每1000平方米膜中1mm以上的缺陷数为1.0个以下
2.根据1.所述的聚酯膜,其使用了聚酯原料,所述聚酯原料的特征在于,在聚酯树脂中含有选自铝化合物中的至少1种和选自磷化合物中的至少1种作为聚合催化剂。
3.根据1.或2.中任一项所述的聚酯膜,其中,膜的雾度为1%以上且8%以下。
4.根据1.~3.中任一项所述的聚酯膜,其特征在于,在150℃·15分钟的条件下测定的纵向的热收缩率为0.8%以上且3%以下。
5.根据1.~4.中任一项所述的聚酯膜,其特征在于,利用连续接触式厚度计遍及1m长测定的纵向和横向的厚度不均的值均为1%以上且10%以下。
6.一种包装袋,其是使用1层以上的上述1.~5.中任一项所述的双轴拉伸聚酯膜而成的。
7.一种标签,其是使用1层以上的上述1.~5.中任一项所述的双轴拉伸聚酯膜而成的。
8.一种制造1.~5.中任一项所述的双轴拉伸聚酯膜的方法,其特征在于,以原料聚酯树脂的特性粘度与聚酯膜的特性粘度之差成为0.06dl/g以下的方式将原料聚酯树脂熔融挤出,接着进行冷却固化而得到未拉伸膜后,将该未拉伸膜进行双轴拉伸,接着进行热固定处理。
发明的效果
根据本发明,提供锑含量极少,另外异物也少,具有优异的透明性、耐热性,并且印刷加工适应性和印刷外观也优异的双轴拉伸聚酯膜和将该膜卷绕而成的膜卷的制造方法。
具体实施方式
以下,对本发明的实施方式进行叙述,但本发明不应被解释为限定于包含以下的实施例的实施方式,当然可以在能够实现发明的目的且不脱离发明的主旨的范围内进行各种变更。
(原料聚酯树脂)
本发明的双轴拉伸聚酯膜以聚对苯二甲酸乙二醇酯系树脂作为构成成分。在此,聚对苯二甲酸乙二醇酯系树脂含有来自于乙二醇的成分和来自于对苯二甲酸的成分作为主要构成成分。“主要构成成分”是指在构成聚酯的二羧酸全部成分100摩尔%中,对苯二甲酸为80摩尔%以上,在二醇全部成分100摩尔%中,乙二醇为80摩尔%以上。
只要在不妨碍本发明目的范围内,也可以使其他二羧酸成分和二醇成分共聚。其它二羧酸成分和二醇成分的共聚量相对于全部二羧酸成分或全部二醇成分分别小于20摩尔%,优选为10摩尔%以下,特别优选为5摩尔%以下。
作为上述其他二羧酸成分,可举出间苯二甲酸、邻苯二甲酸、萘二甲酸、4,4’-二羧基联苯、间苯二甲酸-5-磺酸钠等芳香族二羧酸、1,4-环己烷二甲酸、1,3-环己烷二甲酸、1,2-环己烷二甲酸、2,5-降冰片烯二甲酸、四氢邻苯二甲酸等脂环族二羧酸、草酸、丙二酸、琥珀酸、己二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、十八烷二酸、富马酸、马来酸、衣康酸、中康酸、柠康酸、二聚酸等脂肪族二羧酸等。
作为上述其他二醇成分,可举出1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、2-氨基-2-乙基-1,3-丙二醇、2-氨基-2-甲基-1,3-丙二醇、1,10-癸二醇、二羟甲基三环癸烷、二乙二醇、三乙二醇等脂肪族二醇、双酚A、双酚S、双酚C、双酚Z、双酚AP、4,4’-联苯酚的环氧乙烷加成物或环氧丙烷加成物、1,2-环己烷二甲醇、1,3-环己烷二甲醇、1,4-环己烷二甲醇等脂环族二醇、聚乙二醇、聚丙二醇等。
作为这样的聚对苯二甲酸乙二醇酯系树脂的聚合法,可以利用使对苯二甲酸与乙二醇、以及根据需要的其他二羧酸成分和二醇成分直接反应的直接聚合法、以及对苯二甲酸的二甲酯(根据需要包含其他二羧酸的甲酯)与乙二醇(根据需要包含其他二醇成分)进行酯交换反应后进行缩聚反应的酯交换法等任意的制造方法。
作为聚酯树脂,也可以使用对PET瓶进行再生利用而得到的再循环树脂、包含来自于生物质的单体成分的聚酯树脂。
作为本发明的双轴拉伸聚酯膜的构成成分,可以包含聚酰胺、聚苯乙烯、聚烯烃、以及上述以外的聚酯等其他树脂,从双轴拉伸聚酯膜的机械特性、耐热性的方面考虑,其他树脂的含量相对于聚酯膜的全部树脂成分为30质量%以下,进一步优选为20质量%以下,另外进一步优选为10质量%以下,特别优选为5质量%以下,最优选为0质量%(构成聚酯膜的全部树脂成分实质上为聚对苯二甲酸乙二醇酯系树脂)。
另外,上述聚对苯二甲酸乙二醇酯系树脂的特性粘度优选为0.57~0.76dl/g的范围,更优选为0.60~0.73dl/g,进一步优选为0.63~0.7dl/g。如果特性粘度低于0.57dl/g,则在聚酯膜生产过程中膜容易破裂(产生所谓断裂),如果高于0.76dl/g,则滤压上升变大,高精度过滤变得困难,经由过滤器挤出树脂容易变得困难。
另外,上述聚酯膜的树脂的特性粘度优选为0.51~0.70dl/g的范围,更优选为0.56~0.68dl/g,进一步优选为0.59~0.65dl/g。如果特性粘度低于0.51dl/g,则聚酯膜在印刷等加工工序容易破裂,如果特性粘度高于0.76dl/g,则提高机械特性的效果容易成为饱和状态。
(聚合催化剂)
接下来,对制造本发明中使用的原料聚酯树脂时使用的聚合催化剂进行说明。本发明中使用的聚合催化剂是以具有促进酯化的能力为特征的聚合催化剂。在本发明中,如后所述,优选尽可能不使用以往使用的三氧化锑等锑化合物的聚合催化剂。作为这样的聚合催化剂,优选包含选自铝化合物中的至少1种和选自磷系化合物中的至少1种的聚合催化剂。
在合成本发明中使用的原料聚酯树脂时,作为构成所使用的聚合催化剂的铝化合物,可以没有限定地使用公知的铝化合物。
作为铝化合物,具体而言,可举出乙酸铝、碱性乙酸铝、乳酸铝、氯化铝、氢氧化铝、氢氧化氯化铝和乙酰丙酮铝、草酸铝等有机铝化合物和它们的部分水解物等。其中,优选羧酸盐、无机酸盐和螯合物化合物,其中,更优选乙酸铝、碱性乙酸铝、乳酸铝、氯化铝、氢氧化铝、氢氧化氯化铝和乙酰丙酮铝,进一步优选乙酸铝、碱性乙酸铝、氯化铝、氢氧化铝和氢氧化氯化铝,最优选乙酸铝、碱性乙酸铝。
本发明的聚合催化剂中使用的铝化合物的使用量以铝原子计,相对于所得到的聚酯树脂的总质量,优选残留1~80ppm,更优选为2~60ppm,进一步优选为3~50ppm,特别优选为5~40ppm,最优选为10~30ppm。
如果低于上述,则有可能催化活性变得不良,如果超过上述,则有可能引起铝系异物生成。
铝化合物即使在聚酯聚合时置于减压环境下,使用量的几乎100%也会残留,因此可以认为使用量成为残留量。
聚合催化剂中使用的磷化合物没有特别限定,如果使用膦酸系化合物、次膦酸系化合物,则催化活性的提高效果大,因此优选,其中,如果使用膦酸系化合物,则催化活性的提高效果特别大,因此优选。
这些磷化合物中,优选在同一分子内具有酚部的磷化合物。只要是具有酚结构的磷化合物就没有特别限定,如果使用在同一分子内具有酚部的、选自膦酸系化合物、次膦酸系化合物中的一种或两种以上的化合物,则催化活性的提高效果大,因此优选。其中,如果使用一种或两种以上的在同一分子内具有酚部的膦酸系化合物,则催化活性的提高效果特别大,因此优选。
另外,作为在同一分子内具有酚部的磷化合物,可举出下述通式(化学式1)、(化学式2)所示的化合物等。
[化学式1]
P(=O)R1(OR2)(OR3)
[化学式2]
P(=O)R1R4(OR2)
(式(化学式1)~(化学式2)中,R1表示包含酚部的碳原子数1~50的烃基、羟基或卤素基团或烷氧基或氨基等取代基和包含酚部的碳原子数1~50的烃基。R4表示氢、碳原子数1~50的烃基、包含羟基或卤素基团或烷氧基或氨基等取代基的碳原子数1~50的烃基。R2、R3各自独立地表示氢、碳原子数1~50的烃基、包含羟基或烷氧基等取代基的碳原子数1~50的烃基。其中,烃基可以包含支链结构、环己基等脂环结构、苯基、萘基等芳香环结构。R2与R4的末端彼此可以键合。)
作为上述的在同一分子内具有酚部的磷化合物,例如可举出对羟基苯基膦酸、对羟基苯基膦酸二甲酯、对羟基苯基膦酸二乙酯、对羟基苯基膦酸二苯酯、双(对羟基苯基)次膦酸、双(对羟基苯基)次膦酸甲酯、双(对羟基苯基)次膦酸苯酯、对羟基苯基苯基次膦酸、对羟基苯基苯基次膦酸甲酯、对羟基苯基苯基次膦酸苯酯、对羟基苯基次膦酸、对羟基苯基次膦酸甲酯、对羟基苯基次膦酸苯酯等。此外,可举出下述通式(化学式3)所示的磷化合物。
[化学式3]
式(化学式3)中,X1、X2分别表示氢、碳原子数1~4的烷基、或1价以上的金属。
另外,X1的金属为2价以上,X2可以不存在。此外,也可以相对于磷化合物配置相当于金属的剩余的价数的阴离子。
作为金属,优选Li、Na、K、Ca、Mg、Al。
通过在聚酯的聚合时添加这些在同一分子内具有酚部的磷化合物,从而铝化合物的催化活性提高,并且聚合后的共聚聚酯树脂的热稳定性也提高。
上述之中,优选用作缩聚催化剂的磷化合物为选自化学式(化学式4)、化学式(化学式5)所示的化合物中的至少一种磷化合物。
[化学式4]
[化学式5]
作为上述化学式(化学式4)所示的化合物,市售有Irganox1222(BASF公司制)。另外,作为化学式(化学式5)所示的化合物,市售有Irganox1425(BASF公司制),可以使用。
本发明的聚合催化剂中使用的磷化合物的使用量以磷原子计,相对于所得到的原料聚酯树脂的总质量,优选残留10~100ppm,更优选为15~90ppm,进一步优选为20~80ppm,特别优选为25~70ppm,最优选为30~60ppm。
超过上述的上下限的量的磷原子残留时,有可能使聚合活性降低。
磷化合物在聚酯聚合时置于减压环境下时,根据该条件,使用量的约10~30%被除去至体系外。因此,实际上需要进行数次试行实验,在确认磷化合物在聚酯中的残留率的基础上决定使用量。
另外,通过使用上述磷化合物,能够提高树脂的耐热性。原因尚不确定,但认为是由于磷化合物中的受阻酚部分而使聚酯树脂的耐热性提高。
如果磷化合物的残留量少于10ppm,则上述耐热性提高的效果减弱,结果,有时观察不到本发明的聚酯树脂的耐热性、着色改善效果。
在不损害本发明的效果的范围内,为了进一步提高催化剂活性,可以并用锑化合物、钛化合物、锡化合物、锗化合物等含金属缩聚催化剂。这种情况下,锑化合物相对于所得到的共聚聚酯树脂的质量,以锑原子计优选为10ppm以下,锗化合物相对于所得到的聚酯树脂的质量,以锗原子计优选为10ppm以下,钛化合物相对于所得到的聚酯树脂的质量,以钛原子计优选为3ppm以下,锡化合物相对于所得到的聚酯树脂的质量,以锡原子计优选为3ppm以下。从本发明的目的出发,优选尽可能不使用这些锑化合物、钛化合物、锡化合物、锗化合物等含金属缩聚催化剂。
在本发明中,除了铝化合物以外,还可以使选自少量的碱金属、碱土类金属及其化合物中的至少1种作为第二含金属成分共存。通过使该第二含金属成分在催化剂系中共存,从而除了抑制二乙二醇的生成的效果以外,还提高催化活性,因此能够得到进一步提高了反应速度的催化剂成分,对生产率提高是有效的。在并用添加碱金属、碱土类金属、或它们的化合物的情况下,其使用量(mol%)相对于构成聚酯树脂的二羧酸成分的摩尔数优选为1×10-5~0.01mol%。碱金属、碱土类金属、或它们的化合物即使在聚酯聚合时置于减压环境下,使用量的几乎100%也残留,因此可以认为使用量成为残留量。
本发明的聚合催化剂不仅对缩聚反应具有催化活性,而且对酯化反应和酯交换反应也具有催化活性。对苯二甲酸二甲酯等二羧酸的烷基酯与乙二醇等二醇的酯交换反应通常在锌等酯交换催化剂的存在下进行,也可以使用本发明的催化剂来代替这些催化剂。另外,本发明的聚合催化剂不仅在熔融聚合中具有催化活性,而且在固相聚合、溶液聚合中也具有催化活性。
本发明中使用的聚酯的聚合催化剂可以在聚合反应的任意阶段添加到反应体系中。例如,可以在酯化反应或酯交换反应开始前和反应过程中的任意阶段、缩聚反应即将开始前、或者缩聚反应过程中的任意阶段向反应体系中添加。特别是,本发明的铝化合物和磷化合物的添加优选在缩聚反应即将开始前添加。
(双轴拉伸聚酯系膜的优选的制造方法)
本发明的双轴拉伸聚酯膜可以为1层、2层、3层或4层以上的层叠结构。在2层结构以上的情况下,各层如上所述以聚对苯二甲酸乙二醇酯系树脂、和无机粒子、以及聚对苯二甲酸乙二醇酯系树脂以外的树脂作为构成成分,但优选彼此相邻的各层中的任意构成成分的种类或含量不同。
在由A层形成的单层结构的情况下,本发明中的A层成为双轴拉伸聚酯膜整体。
在包含A层的2层结构的情况下,本发明中的A层成为任一者或两者的层。在包含A层的3层结构的情况下,本发明中的A层成为任意1层或两侧表层的2层。
特别是在3层结构的情况下,即使在内部层中不存在无机粒子,通过仅控制表层部的添加粒子量,也能够控制膜的表面粗糙度,能够进一步减少膜中无机粒子的含量,因此优选。这是因为,还连带改善以下方面:气味成分经由在无机粒子与聚酯树脂的边界形成的空隙(void)而逸出,保香性降低。
此外,在不对膜表面的特性造成不良影响的范围内,在内层部中适时混合使用将制膜工序中产生的边缘部分修剪后的回收原料、或者其他制膜工序的再循环原料等变得容易,在成本方面也有优势。
作为上述无机粒子,例如可以使用二氧化硅、氧化铝、二氧化钛、碳酸钙、高岭土、硫酸钡等。无机粒子的平均粒径在库尔特计数器进行测定时优选为0.05~3.0μm的范围内。膜中的无机粒子含有率的下限优选为0.01重量%,更优选为0.015重量%,进一步优选为0.02重量%。如果低于0.01重量%,则有时滑动性降低。上限优选为1重量%,更优选为0.2重量%,进一步优选为0.1重量%。如果超过1重量%,则有时透明性降低,不太优选。
作为使聚酯中含有无机粒子的方法,例如可举出使无机粒子以规定的比例以浆料的形式分散于作为二醇成分的乙二醇中,在聚酯聚合完结前的任意阶段添加该乙二醇浆料。
在此,在添加粒子时,例如,如果在不使粒子的合成时得到的水溶胶、醇溶胶暂时干燥的情况下添加,则粒子的分散性良好,能够抑制粗大突起的产生,因此优选。
另外,将粒子的水浆料直接与规定的聚酯粒料混合,供给至排气方式的双螺杆混炼挤出机并混炼至聚酯中的方法也是有效的。
在本发明中,优选使挤出机的树脂温度为树脂的熔点+2℃以上且树脂的熔点+6℃以下来进行挤出。如果挤出温度低于熔点+2℃,则树脂不熔融而排出未熔融物,其成为异物,因此不优选。另外,如果在高于熔点+6℃的温度下挤出,则树脂发生热劣化而成为异物产生的原因,因此不优选。
然后,将挤出后的片状的熔融树脂用T模挤出后进行骤冷,由此能够得到未拉伸膜。需要说明的是,作为将熔融树脂骤冷的方法,可以优选采用如下方法:将熔融树脂从T模流延至转鼓上进行骤冷固化,从而得到实质上未取向的树脂片。
另外,在T模上容易附着熔融树脂的升华物(低聚物等),如果附着物掉落,则对于未拉伸片而言成为膜的异物,因此不优选。因此,优选在T模上预先粘贴具有粘合性的片材,以使升华物不易落下,另外,为了即使在冷却辊上附着有异物也不会转印到未拉伸片上,在工作中也利用清洁器进行清扫。
此外,对得到的未拉伸膜进行双轴拉伸,接着进行热固定处理和热松弛处理。通过适当组合以下那样的长度方向和宽度方向的拉伸条件、热固定条件、热松弛条件等制膜条件,能够实现后述的优选的膜特性。以下进行详细说明。
拉伸方法可以为同时双轴拉伸,也可以为逐次双轴拉伸,从制膜速度快、生产率高的方面出发,优选逐次双轴拉伸。以下,对最初实施纵向拉伸、接着实施横向拉伸的基于纵向拉伸-横向拉伸的逐次双轴拉伸法进行说明,但也可以是将顺序颠倒的横向拉伸-纵向拉伸。
作为长度(纵向)方向(以下,有时省略为MD)的拉伸温度,从减少弯曲的方面出发,优选为(Tg+15)~(Tg+55)℃,作为拉伸倍率,优选拉伸至3.3~4.7倍。在拉伸温度高于(Tg+55)℃或低于3.3倍的情况下,虽然弯曲减少,但与长度方向相比,宽度方向的分子取向变得过大,因此取向平衡被破坏,因此不优选。另外,所得到的双轴拉伸聚酯膜的平面性也变差,因此不优选。另一方面,在低于(Tg+15)℃或高于4.7倍的情况下,收缩应力增加,弯曲增加,因此不优选。
另外,在长度方向的拉伸中,在多个辊间多阶段地进行拉伸而不是一个阶段的拉伸的方法中,一边控制拉伸速度一边缓慢地沿长度方向进行拉伸,因此能够降低膜宽度方向上的物性差。从效果、设备方面、成本方面出发,优选两阶段~五阶段拉伸。
在沿宽度(横向)方向(以下,有时省略为TD)进行拉伸的情况下,将未拉伸膜导入至能够用夹具把持膜的两端而进行加热的拉幅机装置,利用热风将膜加热至规定的温度后,一边沿长度方向输送一边扩大夹具间的距离,由此将膜沿宽度方向进行拉伸。
另外,如果宽度方向的拉伸温度低于Tg+5℃,则拉伸时容易产生断裂,因此不优选。另外,如果高于Tg+40℃,则无法进行均匀的宽度方向的拉伸,宽度方向的厚度不均变大,因此膜卷的硬度的偏差变大,因此不优选。更优选为Tg+8℃以上且Tg+37℃以下,进一步优选为Tg+11℃以上且Tg+34℃以下。
宽度方向的拉伸倍率没有特别规定,优选为2倍以上且6倍以下。如果拉伸倍率低于2倍,则物质收支上难以得到高收率,而且力学强度降低,此外由于宽度方向的厚度不均而产生膜卷的硬度的偏差,因此不优选。另外,如果拉伸倍率超过6倍,则拉伸制膜时容易断裂,因此不优选。
作为TD拉伸后的热固定温度(热处理温度),优选为220~245℃。在热固定温度高于245℃的情况下,弯曲增加,因此不优选。另一方面,在低于220℃的情况下,长度方向和宽度方向的热收缩率均变高,蒸镀加工时的热尺寸稳定性变差,因此不优选。另外,在TD拉伸后的热固定温度超过245℃的情况下,弯曲增加,因此不优选。
在热松弛处理工序中,在直至膜因热缓和而收缩为止的期间,有时宽度方向的约束力减少而因自重而松弛,另外,膜因伴随气流而发生膨胀,因此处于膜非常容易上下变动的状况。因此,在该热松弛工序中,根据膜的输送状态,所得到的双轴拉伸聚酯膜的取向角、斜向热收缩率差的变化量大幅变动。作为减轻的方法,例如可举出通过适当调整从上下部的喷嘴吹出的风速,从而保持膜平行。作为宽度方向的热松弛率,优选为4~8%。在热缓和率小于4%的情况下,所得到的双轴拉伸聚酯膜的宽度方向的热收缩率变高,蒸镀加工时的尺寸稳定性变差,因此不优选。另一方面,在热缓和率大于8%的情况下,产生弯曲的增加、松动等,宽度方向的厚度不均变大,因此膜卷的硬度的偏差变大,因此不优选。
利用上述方法拉伸制膜的膜通过卷绕装置进行卷绕,制作主卷。该主卷在之后的分切工序中,一边在膜长度方向上施加张力,一边进一步从卷上施加基于接触辊的压力(以下称为面压),一边被分切成任意的宽度,被卷绕成制品膜卷。
(双轴拉伸聚酯膜的构成和特性)
本发明的双轴拉伸聚酯膜优选膜中的锑的含量为10ppm以下。锑是担心致癌性的物质,因此量越少越优选,优选为5ppm,更优选为0ppm。本发明中使用的原料树脂的锑优选为0ppm,但存在生产时混入的可能性,设为10ppm以下。
本发明的双轴拉伸聚酯膜优选每1000平方米(例如每膜宽度500mm,每膜卷长2000m)中1mm以上的尺寸的缺陷数为1个以下。通过像这样将每1000平方米(m2)的大面积中的1mm以上的尺寸的缺陷数减少至1个以下,从而印刷性变得非常良好。如果由异物导致的缺陷数多,则在印刷中产生油墨脱落而不优选。1mm以上的尺寸的缺陷数越少越优选,更优选为0.5个以下,进一步优选为0.3个以下,特别优选为0.1个以下,最优选为0个。在本发明中,在未预期的故障时有可能混入异物,设为1个以下。
本发明的双轴拉伸聚酯膜优选聚酯树脂的特性粘度与聚酯膜的特性粘度之差为0.06dl/g以下。上述特性粘度之差成为将聚酯树脂熔融挤出时的劣化程度的指标。如果高于0.06dl/g,则在挤出机内树脂劣化而导致产生异物,因此不优选。另外,特性粘度差优选为0dl/g,但由于实质上熔融,所以难以设为0dl/g。优选为0.05dl/g以下,更优选为0.04dl/g以下。
为了像上述那样控制特性粘度之差,在本发明中,优选使挤出机的树脂温度为树脂的熔点+2℃以上且树脂的熔点+6℃以下来进行挤出。如果挤出温度低于熔点+2℃,则树脂不熔融而排出未熔融物,其成为异物,因此不优选。另外,如果在高于熔点+6℃的温度下挤出,则树脂发生热劣化而成为异物,因此不优选。
本发明的双轴拉伸聚酯膜的雾度优选为1%以上且8%以下。如果高于8%,则膜的透明性受损,因此不优选。优选雾度低,但在本发明中,为了赋予滑动性,雾度的下限为1%,因此如此设定。雾度优选为7%以下,更优选为6%以下。
本发明的双轴拉伸聚酯膜优选在150℃·15分钟的条件下测定的热收缩率的纵向为0.8%以上且3%以下。如果热收缩率的纵向高于3%,则在印刷后的工序中干燥时膜收缩,产生印刷图案的偏移等,因此不优选。如果低于0.8%则没有问题,但在本发明的生产方法中0.8%为下限,因此设为0.8%以下。热收缩率的纵向的上限优选为2.5%以下,更优选为2%以下。需要说明的是,该热收缩率的值是利用后述的式(3)算出的值。
本发明的双轴拉伸聚酯膜的遍及1m长度进行测定时的纵向和横向的厚度不均优选膜纵向和横向的厚度不均均为1%以上且10%以下。如果厚度不均大于10%,则在印刷等加工时产生由褶皱导致的印刷脱落、弯曲,因此不优选。膜纵向和横向的厚度不均越低越优选,在本发明中,1%左右为厚度不均的下限。需要说明的是,纵向和横向的厚度不均更优选为8%以下,进一步优选为6%以下。
本发明的双轴拉伸聚酯膜的厚度没有特别规定,优选为2μm以上且300μm以下。如果厚度低于2μm,则膜的硬挺感不足,印刷等加工中容易产生褶皱,另外,硬挺感不足,在制成袋、标签时的工序中容易产生不良情况,因此不优选。厚度厚的部分没有问题,但作为环境、成本应对,与薄壁化所带来的减容化相反,因此厚于300μm是不优选的。厚度更优选为4μm以上且250μm以下,进一步优选为6μm以上且200μm以下。
本发明的双轴拉伸聚酯膜的制品卷的宽度没有特别规定,优选为300mm以上且5000mm以下。如果宽度小于300mm,则印刷、加工中的效率降低,因此不优选。宽度宽是没有问题的,但在印刷、加工工序中,如果宽度过宽,则操作变得大规模,因此不优选比宽度5000mm长。膜卷的宽度更优选为400mm以上且4500mm以下,进一步优选为500mm以上且4000mm以下。
实施例
以下,通过实施例更详细地说明本发明,但本发明不受所述实施例的方式的任何限定,在不脱离本发明的主旨的范围内,可以适当变更。将实施例、比较例中使用的原料的组成、实施例、比较例中的膜的拉伸方式、制造条件分别示于表中。
另外,膜的评价方法如下所述。
[Tg(玻璃化转变温度)、Tm(熔点)]
使用差示扫描量热分析装置(精工电子工业株式会社制,DSC220),将未拉伸膜5mg放入样品盘中,盖上盘盖,在氮气气氛下以10℃/分钟的升温速度从-40℃升温至300℃进行测定。Tg(℃)和Tm(℃)基于JIS-K7121-1987求出。
[特性粘度(IV)]
将聚酯0.2g溶解于苯酚/1,1,2,2-四氯乙烷(60/40(重量比))的混合溶剂50ml中,在30℃下使用奥斯特瓦尔德粘度计进行测定。单位为dl/g。
[聚酯膜中的各种原子的含量]
通过以下所示的方法进行定量。
(a)锑原子
利用硫酸/过氧化氢水的混合液使试样1g湿式分解。接下来,加入亚硝酸钠,使Sb原子为Sb5+,添加亮绿,生成与Sb的蓝色络合物。将该络合物用甲苯提取后,使用吸光光度计(岛津制作所制,UV-150-02),测定波长625nm处的吸光度,根据预先制成的标准曲线对试样中的Sb原子的量进行比色定量。
(b)磷原子
利用使试样1g在碳酸钠共存下进行干式灰化分解的方法、或者利用硫酸/硝酸/高氯酸的混合液或硫酸/过氧化氢水的混合液进行湿式分解的方法,将磷化合物制成正磷酸。接下来,在1摩尔/L的硫酸溶液中使钼酸盐反应而形成磷钼酸,将其用硫酸肼还原而生成杂多蓝。利用吸光光度计(岛津制作所制,UV-150-02)测定波长830nm处的吸光度。根据预先制成的标准曲线对试样中的磷原子的量进行定量。
(c)铝原子
将试样0.1g溶解于6M盐酸溶液中,放置一天后,用纯水稀释,制成1.2M盐酸测定用溶液。通过高频等离子体发光分析求出制备的溶液试样。
[缺陷数]
使用放卷机将宽度800mm、卷长10000m(8000平方米)的膜卷放卷。放卷时使用FUTEC公司制的缺陷检测机(型号F MAX MR)调查缺陷数。然后,求出纵向或横向中任一方向上1mm以上的尺寸的缺陷数。根据式(1),根据全部缺陷数求出每1000平方米的缺陷数。
每1000平方米的缺陷数=全部缺陷数÷8 (式1)
[印刷]
对于进行了缺陷检查的800mm、卷长10000m(8000平方米)的膜卷,使用凹版印刷机(东谷铁工所公司制),以速度100m/min、网点5%实施凹版印刷。此时的墨液为凹版印刷墨液(东洋墨液公司制:商品名FineStar R92墨),使用以77:23的比率混合了稀释溶剂(东洋墨液公司制:商品名SL302)的墨液。使用放卷机将所得到的印刷样品放卷。放卷时使用FUTEC公司制的缺陷检测机(型号F MAX MR)调查印刷遗漏数。然后,在纵向或横向中的任一方向上求出1mm以上的尺寸的印刷遗漏数。根据式(2),根据全部印刷遗漏数求出每1000平方米的缺陷数。
每1000平方米的印刷遗漏数=全部缺陷数÷8 (式2)
[热收缩率]
以横向宽度10mm、纵向220mm的尺寸进行采样,在纵向以200mm的间隔标记标线,测定标线的间隔(L0)后,将该膜夹在纸之间,放入到控制为150℃的温度的热风烘箱中,处理15分钟后,取出后,测定标线的间隔(L),根据式(3)求出热收缩率。其他按照JIS-C-2318进行。
热收缩率(%)={(L0-L)/L0}×100 (式3)
[雾度]
依据JIS K 7105在23℃下测定。使用雾度计(日本电色工业株式会社制,300A)进行测定。需要说明的是,测定进行2次,求出其平均值。
[厚度不均]
将膜以沿测定方向1m×沿宽度方向40mm的长条状取样,使用微米测定器株式会社制的连续接触式厚度计,以5(m/分钟)的速度连续地测定膜试样的厚度。根据下式4算出膜的厚度不均。
厚度不均=(最大厚度-最小厚度)÷平均厚度×100(%) (式4)
<聚合催化剂溶液的制备>
(磷化合物的乙二醇溶液)
在具备氮导入管、冷凝管的烧瓶中,在常温常压下加入乙二醇2.0升后,一边在氮气氛下以200rpm搅拌,一边加入作为磷化合物的化学式(4)所示的Irganox1222(BASF公司制)200g。进一步追加2.0升的乙二醇后,将夹套温度的设定变更为196并升温,从内温达到185以上的时刻起在回流下搅拌60分钟。然后停止加热,立即将溶液从热源去除,在保持氮气氛下的状态下,在30分钟以内冷却至120℃以下。
(铝化合物的乙二醇溶液)
在具备冷凝管的烧瓶中,在常温常压下加入纯水5.0升后,一边以200rpm搅拌,一边以与纯水的浆料的形式加入碱性乙酸铝(羟基二乙酸铝)200g。此外,以整体成为10.0升的方式追加纯水,在常温常压下搅拌12小时。然后,将夹套温度的设定变更为100.5℃并升温,从内温成为95℃以上的时刻起在回流下搅拌3小时。停止搅拌,放冷至室温。这时,观察到未溶解粒子时,将溶液用玻璃过滤器(3G)过滤,得到铝化合物的水溶液。
接着,在常温常压下向具备蒸馏装置的烧瓶中投入上述铝化合物的水溶液2.0升和乙二醇2.0升,以200rpm搅拌30分钟后,得到均匀的水/乙二醇混合溶液。接下来,将夹套温度的设定变更为110℃并升温,从该溶液中蒸馏除去水。在馏出的水的量达到2.0升的时刻停止加热,放冷至室温,由此得到铝化合物的乙二醇溶液。
以下,“份”表示“质量份”。
在装备有搅拌机、温度计、馏出用冷却机的反应罐中添加对苯二甲酸2130份、乙二醇1955份、三乙胺0.7份,在0.35MPa的加压下,从220℃缓慢升温至250,一边将馏出的水除去至体系外一边进行酯化反应。接着,对于上述聚合催化剂溶液,以相对于聚酯树脂中的二羧酸成分以磷原子计成为0.047摩尔%、以铝原子计成为0.021摩尔%的方式添加磷化合物的乙二醇溶液和铝化合物的乙二醇混合溶液后,用1小时进行减压初期聚合至1.3kPa,并且上升至270,进一步在0.13kPa以下进行后期聚合,得到聚酯1。
在上述聚酯1的制造方法中,如下所述进行一部分变更而制造聚酯2和3。将各聚酯的组成和物性示于表1。
实施例和比较例中使用的聚酯如下所述。
·聚酯1:聚对苯二甲酸乙二醇酯(IV 0.73dl/g)
·聚酯2:上述聚酯1的制造时,以相对于聚酯为8000ppm的比例添加了作为润滑剂的SiO2(FUJI SILYSIA公司制Sylysia 266)的聚对苯二甲酸乙二醇酯(IV 0.73dl/g)
·聚酯3:在上述聚酯1的制造时,以成为0.084摩尔%的方式添加锑催化剂来代替铝(IV 0.73dl/g)
[表1]
DMT:对苯二甲酸二甲酯
EG:乙二醇
〔实施例1〕
将上述聚酯1和聚酯2以重量比97∶3混合并投入到挤出机中。然后,使该混合树脂在270℃下熔融,冷却至260℃,从T模挤出,卷绕于表面温度冷却至30℃的旋转的金属辊并骤冷,由此得到厚度为220μm的未拉伸膜。此时的未拉伸膜的牵引速度(金属辊的旋转速度)约为80m/min。未拉伸膜的Tg为75℃,Tm为256℃。另外,在T模上粘贴由高熔点聚酰亚胺制作的粘合片,使熔融树脂的挥发物不落下。另外,为了除去落下到冷却辊上的异物,使用UV照射型的清洁器。
将所得到的未拉伸片加热至115℃,通过将第一阶段设为1.24倍、将第二阶段设为1.4倍、将第三阶段设为2.6倍的三阶段拉伸,以总拉伸倍率4.5倍沿长度方向进行拉伸。接着,以温度140℃、拉伸倍率4.3倍沿宽度方向进行拉伸,在243℃下进行热固定,沿宽度方向进行5%热松弛处理。接下来,将该拉伸后的膜的两端部裁切除去后,经过电晕放电处理,用卷绕机卷绕成卷状,制作厚度12μm、宽度8m的双轴拉伸聚酯膜的主卷。
通过上述方法对所得到的膜的特性进行评价。另外,关于缺陷数的评价,利用分切成宽度800mm、卷长10000m而得到的卷,利用上述方法进行评价。将膜的制造方法示于表2,将评价结果示于表3。是能够确保卫生性的充分低的锑量、缺陷数少的印刷外观优异的良好的膜。
〔实施例2〕
将聚酯1和聚酯2以重量比99.5∶0.5混合并投入到挤出机中,除此以外,通过与实施例1相同的方法得到双轴拉伸聚酯膜卷。将膜的制造方法示于表2,将评价结果示于表3。与实施例1相比,是透明性优异的良好品质的膜。另外,印刷遗漏也少,是良好的。
〔实施例3〕
将聚酯1、聚酯2与聚酯3以重量比96.5∶3∶0.5混合并投入到挤出机中,除此以外,利用与实施例1相同的方法得到双轴拉伸聚酯膜卷。将膜的制造方法示于表2,将评价结果示于表3。与实施例1相比锑量稍微增加,缺陷数稍微增加,但为充分少的缺陷数,是良好品质的膜。
〔比较例1〕
将聚酯3与聚酯2以重量比97∶3混合并投入到挤出机中。除此以外,利用与实施例1相同的方法得到双轴拉伸聚酯膜卷。将膜的制造方法示于表2,将评价结果示于表3。与实施例1相比锑量增加,缺陷数增加,是品质差的膜。另外,印刷遗漏也比实施例1多而成为差的结果。
〔比较例2〕
将聚酯1、聚酯2与聚酯3以重量比48.5∶3∶48.5混合并投入到挤出机中。然后,使该混合树脂在280℃下熔融,冷却至270℃,从T模挤出,除此以外,通过与实施例1同样的方法得到双轴拉伸聚酯膜。利用与实施例1相同的方法对所得到的膜的特性进行评价。将膜的制造方法示于表2,将评价结果示于表3。评价的结果为特性粘度的降低大、缺陷数也增加、品质差的双轴拉伸聚酯膜。
[表2]
[表3]
产业上的可利用性
本发明的双轴拉伸聚酯膜是锑的量极少、且印刷性、加工性、生产率良好的双轴拉伸聚酯膜,因此是适合于卫生性优异的食品包装袋、标签的膜。
Claims (8)
1.一种双轴拉伸聚酯膜,其特征在于,满足下述要件(1)~(4):
(1)膜中的锑的含量为10ppm以下,
(2)膜中的磷的含量为25ppm以上且75ppm以下,
(3)膜的特性粘度为0.51dl/g以上且0.70dl/g以下,
(4)每1000平方米膜中,1mm以上的缺陷数为1.0个以下。
2.根据权利要求1所述的聚酯膜,其使用了聚酯原料,所述聚酯原料的特征在于,在聚酯树脂中含有选自铝化合物中的至少1种和选自磷化合物中的至少1种作为聚合催化剂。
3.根据权利要求1或2中任一项所述的聚酯膜,其中,膜的雾度为1%以上且8%以下。
4.根据权利要求1~3中任一项所述的聚酯膜,其特征在于,在150℃·15分钟的条件下测定的纵向的热收缩率为0.8%以上且3%以下。
5.根据权利要求1~4中任一项所述的聚酯膜,其特征在于,利用连续接触式厚度计遍及1m长度测定的纵向和横向的厚度不均的值均为1%以上且10%以下。
6.一种包装袋,其是使用1层以上的权利要求1~5中任一项所述的双轴拉伸聚酯膜而成的。
7.一种标签,其是使用1层以上的权利要求1~5中任一项所述的双轴拉伸聚酯膜而成的。
8.一种制造权利要求1~5中任一项所述的双轴拉伸聚酯膜的方法,其特征在于,以原料聚酯树脂的特性粘度与聚酯膜的特性粘度之差成为0.06dl/g以下的方式将原料聚酯树脂熔融挤出,接着进行冷却固化而得到未拉伸膜后,对该未拉伸膜进行双轴拉伸,接着进行热固定处理。
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TW202045598A (zh) | 2020-12-16 |
US20220056223A1 (en) | 2022-02-24 |
KR20210127720A (ko) | 2021-10-22 |
JP7380601B2 (ja) | 2023-11-15 |
WO2020166353A1 (ja) | 2020-08-20 |
EP3925758A1 (en) | 2021-12-22 |
TWI833890B (zh) | 2024-03-01 |
JP2023184602A (ja) | 2023-12-28 |
EP3925758A4 (en) | 2022-08-24 |
JPWO2020166353A1 (zh) | 2020-08-20 |
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